CN106046211A

CN106046211A - Metallocene poly-alpha olefin catalyst used for synthesis of lubricant base oil, and preparation method and application thereof

Info

Publication number: CN106046211A
Application number: CN201610044896.2A
Authority: CN
Inventors: 魏东初; 李兵
Original assignee: SUZHOU APAC PHARMACEUTICAL TECHNOLOGY Co Ltd
Current assignee: YAPEIXI TECHNOLOGY (JIAXING) CO., LTD.
Priority date: 2015-01-26
Filing date: 2016-01-22
Publication date: 2016-10-26
Also published as: CN108559012A

Abstract

The invention relates to a metallocene poly-alpha olefin catalyst used for synthesis of lubricant base oil. The structure of the catalyst is composed of following parts: a substituted aryl group, bridged silicon or carbon atoms, a 3-monosubstituted or 3,6-disubstituted fluorenyl group or 3-monosubstituted or 3,6-disubstituted 5H-indeno[1,2-b]pyridyl group or 3-monosubstituted or 3,6-disubstituted 5H-indeno[1,2-b]thiopyranyl group, and metal dentate. The metallocene poly-alpha olefin catalyst provided by the invention is stable in structure and high in catalysis efficiency; and the preparation method is simple to operate, high in yield, low in cost and small in environmental pollution, uses easily available raw materials and can easily realize industrial production.

Description

Synthetic lubricant base oil with metallocene poly-alpha olefins catalyst and preparation method thereof and Application

Technical field

The present invention relates to a kind of catalyst, particularly to a kind of metallocene poly-alpha olefins catalyst and preparation method thereof and should With.

Background technology

Poly alpha olefine synthetic oil (PAO) is the lube base oil of a kind of excellent performance, is current hybrid-engine oil, tooth One of oil base stock that wheel oil is most widely used with in other iundustrial oils, fat, it artificial oil modulated greatly extends Lubricant grease range of application under high temperature, low temperature, high load capacity and other harsh conditions, it is provided that the viscosity temperature characteristic of excellence, heat Oxidation stability, lubrication and wear resistance and detergency, thus greatly extend the oil draining period, slow down equipment corrosion and Abrasion, reduces the maintenance cycle of equipment, greatly increases utilization rate and the service life of equipment, create for user abundant Economic benefit, simultaneously achieve the biggest social benefit in environmental protection and energy-conservation aspect again.Therefore, current many most high-grade In lubricating oil product, PAO is the most generally particularly preferred as the base oil of lubricating oil.

ExxonMobil company is one of dominant company of produced worldwide poly alpha olefin, and in May, 2010 is proposed use The high viscosity poly alpha olefin SpectraSyn Elite of new generation of metallocene catalyst synthesis technique synthesis, for being different from routine PAO, this new PAO base oil is referred to as mPAO.PAO molecule has prominent backbone under normal circumstances, from backbone with unordered Mode stretches out side chain different in size.Its molecular structure can show as following.And mPAO uses metallocene catalyst synthesis technique, Metallocene is single site catalysts, and the geometry of its uniqueness the most homogeneous available chemical products, so mPAO has , there is not upright side chain in pectinate texture.This shape has rheological behavior and the flow performance of improvement compared with conventional PAO, Thus can preferably provide shear stability, relatively low pour point and higher viscosity index (VI), especially because there is less side chain And there is the shear stability more much higher than conventional PAO.It is answering of high severity that these characteristics determine the use target of mPAO With, including power drive system and gear oil, compressor lubricant oil, transmission fluid and industrial lubricant.

The synthesis about mPAO abroad starts to walk relatively early with exploitation, and each major company of the world such as Mobil, Chemtura and BP etc. have The patent of oneself, especially Mobil, Chevron Corporation (Stardard Oil Company of California) and Japan go out light and have been realized in industrialized production in the recent period and release to market The product of oneself, concrete condition is as shown in table 1.Domestic in terms of PAO synthesis it is constantly in backward situation, in recent years Shanghai Nanogram Corp. and Fu Ke lion company just complete the research and development of the PAO synthetic technology with independent intellectual property right and have Related product Release.But about the rare relevant research of research and development and the report of mPAO, the research and development in this field at present are substantially at blank.

The performance of poly alpha olefine synthetic oil except having with polymer raw outside the Pass, largely by its synthetic catalyst and conjunction Technique is become to be determined.At present, the synthesis of main flow PAO product uses non-single site catalysts, obtained product knot mostly Structure is the most neat, so compared with single active center metallocene catalyst sintetics, viscosity temperature characteristic having a certain distance.Close The metallocene catalyst becoming mPAO mainly has two big classes: non-bridged combined metal catalyst and means of special bridged metallocene catalysts.Use non- Product synthesized by means of special bridged metallocene catalysts is low viscous PAO in being, uses obtained by means of special bridged metallocene catalysts then PAO for medium-high viscosity.

Summary of the invention

It is an object of the invention to: provide the synthetic lubricant base oil metallocene poly-alpha olefins of a kind of new structure to be catalyzed Agent and its preparation method and application, mainly with bridging silicon or carbon atom, 3 monosubstituted or 3,6 dibasic fluorenyls or 5H-indeno [1,2-b] pyridine radicals or the transistion metal compound of 5H-indeno [1,2-b] thiopyranyl.

The technical scheme realizing the object of the invention is:

A kind of synthetic lubricant base oil metallocene poly-alpha olefins catalyst, its structure is by substituted aromatic base, bridging silicon Or carbon atom, 3 monosubstituted or 3,6 dibasic fluorenyls or 5H-indeno [1,2-b] pyridine radicals or 5H-indeno [1, 2-b] thiopyranyl, metal-complexing base five part forms:

X=C, S, N

Y=Si, C

M=Zr, Hf, Ti

Wherein: R₁It is the substituent group on cyclopentadiene, for fluorine atom or hydrogen atom；

R₂It is substituent group on benzothiophene, for fluorine atom or hydrogen atom；R₃Substituent group on indole, for fluorine atom or Hydrogen atom；R₄It is the substituent group on the silicon atom of bridging, for cyclohexyl, cyclopenta, cyclobutyl；When bridge formation atom is carbon, take Dai Jiwei 1,3,5-tri-replacement or monosubstituted dibasic phenyl；

R₅It is the 3 monosubstituted or 3 of fluorenyl or 5H-indeno [1,2-b] pyridine radicals or 5H-indeno [1,2-b] thiopyranyl, Bis-substituted substituent groups of 6-, R₅It is one of all straight chains of carbon number 2～24, the alkane of side chain, halogen；

M is metal zirconium or hafnium or titanium；

L is the halogen with metal-complexing.

L is the halogen with metal-complexing, and the price according to metal is different, and halogen substiuted number is different

Described R₅It is:

1) fluorenyl: 3-fluorine fluorenyl, 3,6-difluoro fluorenyl, 3-bromine fluorenyl, 3,6-dibromo fluorenyl, 3-iodine fluorenyl, 3,6-diiodo- Fluorenyl, 3-ethylfluorenyl, 3,6-diethyl fluorenyl, 3-propyl group fluorenyl, 3,6-dipropyl fluorenyl, 3-butyl base fluorenyl, 3,6-bis- Butyl fluorenyl, 3-isopropyl fluorenyl, 3,6-diisopropyl fluorenyl, 3-isobutyl group base fluorenyl, 3,6-diisobutyl fluorenyl, 3-amyl group Fluorenyl, 3,6-diamyl fluorenyl, 3-isopentyl fluorenyl, 3,6-diisoamyl fluorenyl, 3-tert-butyl group base fluorenyl, 3, the tertiary fourth of 6-bis- Base base fluorenyl, 3-pi-allyl fluorenyl, 3,6-diallyl base fluorenyl, 3-hexyl fluorenyl, 3,6-dihexyl fluorenyl, 3-isohesyl fluorenes Base, 3,6-bis-isohesyl fluorenyl, 3-t-butylethyl fluorenyl, 3,6-di-t-butyl ethylfluorenyl, 3-heptyl fluorenyl, 3,6-bis-heptan Base fluorenyl, 3-different heptyl fluorenyl, 3,6-bis-different heptyl fluorenyl, 3-tert-butyl group propyl group fluorenyl, 3,6-di-t-butyl propyl group fluorenyl, 3- Octyl group fluorenyl, 3,6-dioctyl fluorenyl, 3-iso-octyl fluorenyl, 3,6-diisooctyl fluorenyl, 3-tert-butyl group butyl fluorenyl, 3,6-bis- Tert-butyl group butyl fluorenyl, 3-undecyl fluorenyl, 3,6-bis--undecyl fluorenyl, 3-dodecyl fluorenyl, 3,6-bis--ten two Alkyl fluorenyl, 3-tridecyl fluorenyl, 3,6-bis--tridecyl fluorenyl, 3-myristyl fluorenyl, 3,6-bis--myristyl fluorenes Base, 3-pentadecyl fluorenyl, 3,6-bis--pentadecyl fluorenyl, 3-cetyl fluorenyl, 3,6-bis--cetyl fluorenyl, 3-ten Seven alkyl fluorenyls, 3,6-bis--heptadecyl fluorenyl, 3-octadecyl fluorenyl, 3,6-bis--octadecyl fluorenyl, 3-nonadecyl Fluorenyl, 3,6-bis--nonadecyl fluorenyl, 3-eicosyl fluorenyl, 3,6-bis--eicosyl fluorenyl, 3-heneicosyl fluorenyl, 3,6-bis--heneicosyl fluorenyls, 3-docosyl fluorenyl, 3,6-bis--docosyl fluorenyl, 3-tricosyl fluorenes Base, 3,6-bis--tricosyl fluorenyl, 3-tetracosyl fluorenyl, 3, one of 6-bis--tetracosyl fluorenyl；

2) 5H-indeno [1,2-b] pyridine radicals: 3-fluorine 5H-indeno [1,2-b] pyridine radicals, 3,6-difluoro 5H-indeno [1,2- B] pyridine radicals, 3-bromine 5H-indeno [1,2-b] pyridine radicals, 3,6-dibromo 5H-indeno [1,2-b] pyridine radicals, 3-iodine 5H-indeno [1, 2-b] pyridine radicals, 3,6-diiodo-5H-indeno [1,2-b] pyridine radicals, 3-ethyl 5H-indeno [1,2-b] pyridine radicals, 3,6-diethyl 5H-indeno [1,2-b] pyridine radicals, 3-propyl group 5H-indeno [1,2-b] pyridine radicals, 3,6-dipropyl 5H-indeno [1,2-b] pyridine Base, 3-butyl 5H-indeno [1,2-b] pyridine radicals, 3,6-dibutyl 5H-indeno [1,2-b] pyridine radicals, 3-isopropyl 5H-indeno [1,2-b] pyridine radicals, 3,6-diisopropyl 5H-indeno [1,2-b] pyridine radicals, 3-isobutyl group base 5H-indeno [1,2-b] pyridine Base, 3,6-diisobutyl 5H-indeno [1,2-b] pyridine radicals, 3-amyl group 5H-indeno [1,2-b] pyridine radicals, 3,6-diamyl 5H- Indeno [1,2-b] pyridine radicals, 3-isopentyl 5H-indeno [1,2-b] pyridine radicals, 3,6-diisoamyl 5H-indeno [1,2-b] pyridine Base, 3-tert-butyl group 5H-indeno [1,2-b] pyridine radicals, 3,6-di-t-butyl 5H-indeno [1,2-b] pyridine radicals, 3-pi-allyl 5H- Indeno [1,2-b] pyridine radicals, 3,6-diallyl 5H-indeno [1,2-b] pyridine radicals, 3-hexyl 5H-indeno [1,2-b] pyridine Base, 3,6-dihexyl 5H-indeno [1,2-b] pyridine radicals, 3-isohesyl 5H-indeno [1,2-b] pyridine radicals, 3,6-bis-isohesyl 5H-indeno [1,2-b] pyridine radicals, 3-t-butylethyl 5H-indeno [1,2-b] pyridine radicals, 3,6-di-t-butyl ethyl 5H-indeno [1,2-b] pyridine radicals, 3-heptyl 5H-indeno [1,2-b] pyridine radicals, 3,6-diheptyl 5H-indeno [1,2-b] pyridine radicals, 3-are different Heptyl 5H-indeno [1,2-b] pyridine radicals, 3,6-bis-different heptyl 5H-indeno [1,2-b] pyridine radicals, 3-tert-butyl group propyl group 5H-indeno [1,2-b] pyridine radicals, 3,6-di-t-butyl propyl group 5H-indeno [1,2-b] pyridine radicals, 3-octyl group 5H-indeno [1,2-b] pyridine Base, 3,6-dioctyl 5H-indeno [1,2-b] pyridine radicals, 3-iso-octyl 5H-indeno [1,2-b] pyridine radicals, 3,6-diisooctyl 5H-indeno [1,2-b] pyridine radicals, 3-tert-butyl group butyl 5H-indeno [1,2-b] pyridine radicals, 3,6-di-t-butyl butyl 5H-indeno [1,2-b] pyridine radicals, 3-undecyl 5H-indeno [1,2-b] pyridine radicals, 3,6-bis--undecyl 5H-indeno [1,2-b] pyrrole Piperidinyl, 3-dodecyl 5H-indeno [1,2-b] pyridine radicals, 3,6-bis--dodecyl 5H-indeno [1,2-b] pyridine radicals, 3-ten Trialkyl 5H-indeno [1,2-b] pyridine radicals, 3,6-bis--tridecyl 5H-indeno [1,2-b] pyridine radicals, 3-myristyl 5H- Indeno [1,2-b] pyridine radicals, 3,6-bis--myristyl 5H-indeno [1,2-b] pyridine radicals, 3-pentadecyl 5H-indeno [1,2- B] pyridine radicals, 3,6-bis--pentadecyl 5H-indeno [1,2-b] pyridine radicals, 3-cetyl 5H-indeno [1,2-b] pyridine radicals, 3,6-bis--cetyl 5H-indeno [1,2-b] pyridine radicals, 3-heptadecyl 5H-indeno [1,2-b] pyridine radicals, 3,6-bis--ten Seven alkyl 5H-indeno [1,2-b] pyridine radicals, 3-octadecyl 5H-indeno [1,2-b] pyridine radicals, 3,6-bis--octadecyl 5H- Indeno [1,2-b] pyridine radicals, 3-nonadecyl 5H-indeno [1,2-b] pyridine radicals, 3,6-bis--nonadecyl 5H-indeno [1,2- B] pyridine radicals, 3-eicosyl 5H-indeno [1,2-b] pyridine radicals, 3,6-bis--eicosyl 5H-indeno [1,2-b] pyridine radicals, 3-heneicosyl 5H-indeno [1,2-b] pyridine radicals, 3,6-bis--heneicosyl 5H-indeno [1,2-b] pyridine radicals, 3-20 Dialkyl group 5H-indeno [1,2-b] pyridine radicals, 3,6-bis--docosyl 5H-indeno [1,2-b] pyridine radicals, 3-tricosyl 5H-indeno [1,2-b] pyridine radicals, 3,6-bis--tricosyl 5H-indeno [1,2-b] pyridine radicals, 3-tetracosyl 5H-indenes And [1,2-b] pyridine radicals, 3, one of 6-bis--tetracosyl 5H-indeno [1,2-b] pyridine radicals；

3) 5H-indeno [1,2-b] thiopyranyl: 3-fluorine 5H-indeno [1,2-b] thiopyranyl, 3,6-difluoro 5H-indenes And [1,2-b] thiopyranyl, 3-bromine 5H-indeno [1,2-b] thiopyranyl, 3,6-dibromo 5H-indeno [1,2-b] sulfur is for pyrrole Mutter base, 3-iodine 5H-indeno [1,2-b] thiopyranyl, 3,6-diiodo-5H-indeno [1,2-b] thiopyranyl, 3-ethyl 5H- Indeno [1,2-b] thiopyranyl, 3,6-diethyl 5H-indeno [1,2-b] thiopyranyl, 3-propyl group 5H-indeno [1,2-b] Thiopyranyl, 3,6-dipropyl 5H-indeno [1,2-b] thiopyranyl, 3-butyl 5H-indeno [1,2-b] thiopyranyl, 3,6-dibutyl 5H-indeno [1,2-b] thiopyranyl, 3-isopropyl 5H-indeno [1,2-b] thiopyranyl, 3,6-bis-is different Propyl group 5H-indeno [1,2-b] thiopyranyl, 3-isobutyl group 5H-indeno [1,2-b] thiopyranyl, 3,6-diisobutyl 5H- Indeno [1,2-b] thiopyranyl, 3-amyl group 5H-indeno [1,2-b] thiopyranyl, 3,6-diamyl 5H-indeno [1,2-b] Thiopyranyl, 3-isopentyl 5H-indeno [1,2-b] thiopyranyl, 3,6-diisoamyl 5H-indeno [1,2-b] sulfur is for pyrrole Mutter base, 3-tert-butyl group base 5H-indeno [1,2-b] thiopyranyl, 3,6-di-t-butyl 5H-indeno [1,2-b] thiopyranyl, 3-pi-allyl 5H-indeno [1,2-b] thiopyranyl, 3,6-diallyl 5H-indeno [1,2-b] thiopyranyl, 3-hexyl 5H-indeno [1,2-b] thiopyranyl, 3,6-dihexyl 5H-indeno [1,2-b] thiopyranyl, 3-isohesyl 5H-indeno [1,2-b] thiopyranyl, 3,6-bis-isohesyl 5H-indeno [1,2-b] thiopyranyl, 3-t-butylethyl 5H-indeno [1, 2-b] thiopyranyl, 3,6-di-t-butyl ethyl 5H-indeno [1,2-b] thiopyranyl, 3-heptyl 5H-indeno [1,2-b] Thiopyranyl, 3,6-diheptyl 5H-indeno [1,2-b] thiopyranyl, 3-different heptyl 5H-indeno [1,2-b] thio-pyrylium Base, 3,6-bis-different heptyl 5H-indeno [1,2-b] thiopyranyl, 3-tert-butyl group propyl group 5H-indeno [1,2-b] thiopyranyl, 3,6-di-t-butyl propyl group 5H-indeno [1,2-b] thiopyranyl, 3-octyl group 5H-indeno [1,2-b] thiopyranyl, 3,6- Dioctyl 5H-indeno [1,2-b] thiopyranyl, 3-iso-octyl 5H-indeno [1,2-b] thiopyranyl, 3,6-diisooctyl 5H-indeno [1,2-b] thiopyranyl, 3-tert-butyl group butyl 5H-indeno [1,2-b] thiopyranyl, 3,6-di-t-butyl fourth Base 5H-indeno [1,2-b] thiopyranyl, 3-undecyl 5H-indeno [1,2-b] thiopyranyl, 3,6-bis--undecyl 5H-indeno [1,2-b] thiopyranyl, 3-dodecyl 5H-indeno [1,2-b] thiopyranyl, 3,6-bis--dodecyl 5H-indeno [1,2-b] thiopyranyl, 3-tridecyl 5H-indeno [1,2-b] thiopyranyl, 3,6-bis--tridecyl 5H-indeno [1,2-b] thiopyranyl, 3-myristyl 5H-indeno [1,2-b] thiopyranyl, 3,6-bis--myristyl 5H-indeno [1,2-b] thiopyranyl, 3-pentadecyl 5H-indeno [1,2-b] thiopyranyl, 3,6-bis--pentadecyl 5H-indeno [1,2-b] thiopyranyl, 3-cetyl 5H-indeno [1,2-b] thiopyranyl, 3,6-bis--cetyl 5H-indeno [1,2-b] thiopyranyl, 3-heptadecyl 5H-indeno [1,2-b] thiopyranyl, 3,6-bis--heptadecyl 5H-indeno [1,2-b] thiopyranyl, 3-octadecyl 5H-indeno [1,2-b] thiopyranyl, 3,6-bis--octadecyl 5H-indeno [1,2-b] thiopyranyl, 3-nonadecyl 5H-indeno [1,2-b] thiopyranyl, 3,6-bis--nonadecyl 5H-indeno [1,2-b] thiopyranyl, 3-eicosyl 5H-indeno [1,2-b] thiopyranyl, 3,6-bis--eicosyl 5H-indeno [1,2-b] thiopyranyl, 3-heneicosyl 5H-indeno [1,2-b] thiopyranyl, 3,6-bis--heneicosane Base 5H-indeno [1,2-b] thiopyranyl, 3-docosyl 5H-indeno [1,2-b] thiopyranyl, 3,6-bis--two 12 Alkyl 5H-indeno [1,2-b] thiopyranyl, 3-tricosyl 5H-indeno [1,2-b] thiopyranyl, 3,6-bis--two ten Trialkyl 5H-indeno [1,2-b] thiopyranyl, 3-tetracosyl 5H-indeno [1,2-b] thiopyranyl, 3,6-bis--two One of myristyl 5H-indeno [1,2-b] thiopyranyl.

The preparation method of synthetic lubricant base oil metallocene poly-alpha olefins catalyst the most of the present invention,

1) substrate is fluorenyl, includes that step (1) is prepared 3 monosubstituted or 3 during cyclopentadienyl group, and 6-bis-replacement fluorenyl derives Thing；(2) substituted cyclopentadienyl is prepared；(3) preparation replaces fluorenyl/cyclopentadienyl ligand lithium salts；(4) halo hexamethylene is prepared The bridging coordination metal compound of silylation or halo substituted-phenyl, then will replace fluorenyl/cyclopentadienyl ligand lithium salts Diethyl ether solution react with bridging coordination metal compound, to obtain corresponding metallocene poly-alpha olefins catalyst.

The preparation method of synthetic lubricant base oil metallocene poly-alpha olefins catalyst of the present invention, the most described step Suddenly (3) are: monosubstituted or 3,6-bis-substituted fluorene radical derivative is dissolved in ether and mixes with the hexane solution of n-BuLi by 3 Close, then stir several hours；Add equimolar substituted cyclopentadienyl, and mixture stirs more than 12 hours；Then with Water hydrolysis reaction mixture, is dried organic facies and also evaporates solvent, purified, filter, crystallize after obtain substituted fluorene butylcyclopentadiene The ligand of base.

The preparation method of synthetic lubricant base oil metallocene poly-alpha olefins catalyst of the present invention, preferably described Step (4) is: be dissolved in ether by halo hexamethylene silane, and drips n-BuLi wherein, then drips metal halide, After stirring the mixture at least 12 hours, or halo substituted benzene is dissolved in ether, and drips n-BuLi wherein, then Dropping metal halide, after stirring the mixture at least 12 hours, the preparation adding step (3) replaces fluorenyl/cyclopentadienyl group Ligand lithium salts, then through including the post processing of the steps such as extraction, distillation, purification, crystallization, i.e. can get product catalyst.

The application of synthetic lubricant base oil metallocene poly-alpha olefins catalyst of the present invention, it is as synthesis profit The catalyst of lubricant base oil reaction, during reaction, its addition is reaction-ure mixture 0.1～10ppm wt%, preferably 0.2ppm Wt%, 0.5ppmwt%, 0.6ppm wt%, 0.8ppm wt%, 1.0ppm wt%, 1.3ppm wt%, 1.5ppm wt%, 1.8ppm wt%, 2.0ppmwt%, 2.3ppm wt%, 2.5ppm wt%, 3.0ppm wt%, 4ppm wt%, 5ppm Wt%, 6ppm wt%, 7ppm wt%, 8ppm wt%, 9ppm wt%, 10ppm wt%.

2) substrate is fluorenyl, includes that step (1) is prepared 3 monosubstituted or 3 during benzothienyl, and 6-bis-replacement fluorenyl derives Thing；(2) preparation replaces benzothienyl；(3) preparation replaces fluorenyl/benzothienyl ligand lithium salts；(4) halo hexamethylene is prepared The bridging coordination metal compound of silylation or halo substituted-phenyl, then will replace fluorenyl/benzothienyl ligand lithium salts Diethyl ether solution react with cyclohexasilanyl coordination metal compound, to obtain corresponding metallocene poly-alpha olefins catalyst.

The preparation method of synthetic lubricant base oil metallocene poly-alpha olefins catalyst of the present invention, the most described step Suddenly (3) are: monosubstituted or 3,6-bis-substituted fluorene radical derivative is dissolved in ether and mixes with the hexane solution of n-BuLi by 3 Close, then stir several hours；Add equimolar replacement benzothienyl, and mixture stirs more than 12 hours；Then with Water hydrolysis reaction mixture, is dried organic facies and also evaporates solvent, purified, filter, crystallize after obtain replacing fluorenyl benzothiophene The ligand of base.

The preparation method of synthetic lubricant base oil metallocene poly-alpha olefins catalyst of the present invention, preferably described Step (4) is: be dissolved in ether by halo hexamethylene silane, and drips n-BuLi wherein, then drips metal halide, After stirring the mixture at least 12 hours, or halo substituted benzene is dissolved in ether, and drips n-BuLi wherein, then Dropping metal halide, after stirring the mixture at least 12 hours, the preparation adding step (3) replaces fluorenyl/benzothienyl Ligand lithium salts, then through including the post processing of the steps such as extraction, distillation, purification, crystallization, i.e. can get product catalyst.

The application of synthetic lubricant base oil metallocene poly-alpha olefins catalyst of the present invention, it is as synthesis profit Lubricant base oil reaction catalyst, during reaction its addition be reaction-ure mixture 0.1～10ppm wt%, preferably 0.2wt%, 0.5ppm wt%, 0.6ppm wt%, 0.8ppm wt%, 1.0ppm wt%, 1.3ppm wt%, 1.5ppm wt%, 1.8ppm wt%, 2.0ppm wt%, 2.3ppm wt%, 2.5ppm wt%, 3.0ppm wt%, 4ppm wt%, 5ppm Wt%, 6ppm wt%, 7ppm wt%, 8ppm wt%, 9ppm wt%, 10ppm wt%.

3) substrate is fluorenyl, includes that step (1) is prepared 3 monosubstituted or 3,6-bis-substituted fluorene radical derivative during indyl；(2) Prepare substituted indolyl；(3) preparation replaces fluorenyl/indyl ligand lithium salts；(4) halogenated cyclic silylation coordinating metal is prepared Compound, then the diethyl ether solution by replacement fluorenyl/indyl ligand lithium salts is anti-with cyclohexasilanyl coordination metal compound Should, to obtain corresponding metallocene poly-alpha olefins catalyst.

The preparation method of synthetic lubricant base oil metallocene poly-alpha olefins catalyst of the present invention, the most described step Suddenly (3) are: monosubstituted or 3,6-bis-substituted fluorene radical derivative is dissolved in ether and mixes with the hexane solution of n-BuLi by 3 Close, then stir several hours；Add equimolar substituted indolyl, and mixture stirs more than 12 hours；Then with water water Solve reactant mixture, be dried organic facies and also evaporate solvent, purified, filter, crystallize after obtain replacing the coordination of fluorenyl indyl Body.

The preparation method of synthetic lubricant base oil metallocene poly-alpha olefins catalyst of the present invention, preferably described Step (4) is: be dissolved in ether by halo hexamethylene silane, and drips n-BuLi wherein, then drips metal halide, After stirring the mixture at least 12 hours, or halo substituted benzene is dissolved in ether, and drips n-BuLi wherein, then Dropping metal halide, after stirring the mixture at least 12 hours, the preparation adding step (3) replaces fluorenyl/indyl coordination Body lithium salts, then through including the post processing of the steps such as extraction, distillation, purification, crystallization, i.e. can get product catalyst.

4) substrate is fluorenyl, includes that step (1) is prepared 3 monosubstituted or 3,6-bis-during 2,3,4,5-tetra-fluoro-1-methylindenyl Substituted fluorene radical derivative；(2) the fluoro-1-methylindenyl of replacement 2,3,4,5-tetra-is prepared；(3) preparation replacement fluorenyl/2,3,4,5-tetra- Fluoro-1-methylindenyl ligand lithium salts；(4) prepare halogenated cyclic silylation coordination metal compound, then will replace fluorenyl/2, The diethyl ether solution of 3,4,5-tetra-fluoro-1-methylindenyl ligand lithium salts reacts with cyclohexasilanyl coordination metal compound, with To corresponding metallocene poly-alpha olefins catalyst.

The preparation method of synthetic lubricant base oil metallocene poly-alpha olefins catalyst of the present invention, the most described step Suddenly (3) are: monosubstituted or 3,6-bis-substituted fluorene radical derivative is dissolved in ether and mixes with the hexane solution of n-BuLi by 3 Close, then stir several hours；Add equimolar 2,3,4,5-tetra-fluoro-1-methylindenyl, and mixture stir 12 hours with On；Then with water hydrolysis reaction mixture, be dried organic facies and also evaporate solvent, purified, filter, crystallize after obtain replacing fluorenyl The ligand of indyl.

The preparation method of synthetic lubricant base oil metallocene poly-alpha olefins catalyst of the present invention, preferably described Step (4) is: be dissolved in ether by halo hexamethylene silane, and drips n-BuLi wherein, then drips metal halide, After stirring the mixture at least 12 hours, or halo substituted benzene is dissolved in ether, and drips n-BuLi wherein, then Dropping metal halide, after stirring the mixture at least 12 hours, preparation replacement fluorenyl/2 of addition step (3), 3,4,5-tetra- Fluoro-1-methylindenyl ligand lithium salts, then through including the post processing of the steps such as extraction, distillation, purification, crystallization, the most available Product catalyst.

1) substrate is 5H-indeno [1,2-b] pyridine radicals, includes that step (1) prepares substituted-cyclopentadienyl during cyclopentadienyl group Base；(2) 5H-indeno [1,2-b] pyridine radicals/cyclopentadienyl ligand lithium salts is prepared；(3) bridging coordinating metal chemical combination is prepared Thing, is then coordinated the diethyl ether solution of 5H-indeno [1,2-b] pyridine radicals/cyclopentadienyl ligand lithium salts with cyclohexasilanyl Metallic compound reacts, to obtain corresponding metallocene poly-alpha olefins catalyst.

The preparation method of synthetic lubricant base oil metallocene poly-alpha olefins catalyst of the present invention, the most described step Suddenly (3) are: be dissolved in ether by 5H-indeno [1,2-b] pyridinyl derivatives and mix with the hexane solution of n-BuLi, so Several hours of rear stirring；Add equimolar substituted cyclopentadienyl, and mixture stirs more than 12 hours；Then hydrolyze with water Reactant mixture, is dried organic facies and also evaporates solvent, purified, filter, crystallize after obtain 5H-indeno [1,2-b] pyridyl ring The ligand of pentadienyl.

The preparation method of synthetic lubricant base oil metallocene poly-alpha olefins catalyst of the present invention, preferably described Step (4) is: be dissolved in ether by halo hexamethylene silane, and drips n-BuLi wherein, then drips metal halide, After stirring the mixture at least 12 hours, or halo substituted benzene is dissolved in ether, and drips n-BuLi wherein, then Dropping metal halide, after stirring the mixture at least 12 hours, adds preparation 5H-indeno [1, the 2-b] pyridine of step (3) Base/cyclopentadienyl ligand lithium salts, then through including the post processing of the steps such as extraction, distillation, purification, crystallization, the most available Product catalyst.

2) substrate is 5H-indeno [1,2-b] pyridine radicals, includes that step (1) prepares substituted benzene bithiophene during benzothienyl Base；(2) 5H-indeno [1,2-b] pyridine radicals/benzothienyl ligand lithium salts is prepared；(3) bridging coordinating metal chemical combination is prepared Thing, is then coordinated the diethyl ether solution of 5H-indeno [1,2-b] pyridine radicals/benzothienyl ligand lithium salts with cyclohexasilanyl Metallic compound reacts, to obtain corresponding metallocene poly-alpha olefins catalyst.

The preparation method of synthetic lubricant base oil metallocene poly-alpha olefins catalyst of the present invention, the most described step Suddenly (3) are: mixed in ether and with the hexane solution of n-BuLi by 5H-indeno [1,2-b] pyridinium dissolution, then stir several Hour；Add equimolar replacement benzothienyl, and mixture stirs more than 12 hours；Then mix with water hydrolysis Thing, is dried organic facies and also evaporates solvent, purified, filter, crystallize after obtain 5H-indeno [1,2-b] pyridine benzothienyl Ligand.

The preparation method of synthetic lubricant base oil metallocene poly-alpha olefins catalyst of the present invention, preferably described Step (4) is: be dissolved in ether by halo hexamethylene silane, and drips n-BuLi wherein, then drips metal halide, After stirring the mixture at least 12 hours, or halo substituted benzene is dissolved in ether, and drips n-BuLi wherein, then Dropping metal halide, after stirring the mixture at least 12 hours, adds preparation 5H-indeno [1, the 2-b] pyridine of step (3) Base/benzothienyl ligand lithium salts, then through including the post processing of the steps such as extraction, distillation, purification, crystallization, the most available Product catalyst.

The application of synthetic lubricant base oil metallocene poly-alpha olefins catalyst of the present invention, it is as synthesis profit Lubricant base oil reaction catalyst, during reaction its addition be reaction-ure mixture 0.1～10ppm wt%, preferably 0.2wt%, 0.5wt%, 0.6ppm wt%, 0.8ppm wt%, 1.0ppm wt%, 1.3ppm wt%, 1.5ppm wt%, 1.8ppm Wt%, 2.0ppm wt%, 2.3ppm wt%, 2.5ppm wt%, 3.0ppm wt%, 4ppm wt%, 5ppm wt%, 6ppm Wt%, 7ppm wt%, 8ppm wt%, 9ppm wt%, 10ppm wt%.

3) substrate is 5H-indeno [1,2-b] pyridine radicals, includes that step (1) prepares substituted indolyl during indyl；(2) system Standby 5H-indeno [1,2-b] pyridine radicals/indyl ligand lithium salts；(3) halogenated cyclic silylation coordination metal compound is prepared, Then by the diethyl ether solution of 5H-indeno [1,2-b] pyridine radicals/indyl ligand lithium salts and cyclohexasilanyl coordinating metal chemical combination Thing reacts, to obtain corresponding metallocene poly-alpha olefins catalyst.

The preparation method of synthetic lubricant base oil metallocene poly-alpha olefins catalyst of the present invention, the most described step Suddenly (3) are: mixed in ether and with the hexane solution of n-BuLi by 5H-indeno [1,2-b] pyridinium dissolution, then stir several Hour；Add equimolar substituted indolyl, and mixture stirs more than 12 hours；Then with water hydrolysis reaction mixture, Be dried organic facies and also evaporate solvent, purified, filter, crystallize after obtain replacing joining of 5H-indeno [1,2-b] pyridine radicals indyl Position body.

The preparation method of synthetic lubricant base oil metallocene poly-alpha olefins catalyst of the present invention, preferably described Step (4) is: be dissolved in ether by halo hexamethylene silane, and drips n-BuLi wherein, then drips metal halide, After stirring the mixture at least 12 hours, or halo substituted benzene is dissolved in ether, and drips n-BuLi wherein, then Dropping metal halide, after stirring the mixture at least 12 hours, adds preparation 5H-indeno [1, the 2-b] pyridine of step (3) Base/indyl ligand lithium salts, then through including the post processing of the steps such as extraction, distillation, purification, crystallization, i.e. can get product Catalyst.

4) substrate is 5H-indeno [1,2-b] pyridine radicals, includes prepared by step (1) during 2,3,4,5-tetra-fluoro-1-methylindenyl Replace 2,3,4,5-tetra-fluoro-1-methylindenyl；(2) 5H-indeno [1,2-b] pyridine radicals/2,3,4,5-tetra-fluoro-1-methyl indenes are prepared Polymerization of olefin using catalyst body lithium salts；(3) prepare halogenated cyclic silylation coordination metal compound, then will replace 5H-indeno [1,2-b] pyridine Base/2, the diethyl ether solution of 3,4,5-tetra-fluoro-1-methylindenyl ligand lithium salts reacts with cyclohexasilanyl coordination metal compound, To obtain corresponding metallocene poly-alpha olefins catalyst.

The preparation method of synthetic lubricant base oil metallocene poly-alpha olefins catalyst of the present invention, the most described step Suddenly (3) are: be dissolved in ether by 5H-indeno [1,2-b] pyridinyl derivatives and mix with the hexane solution of n-BuLi, so Several hours of rear stirring；Add equimolar 2,3,4,5-tetra-fluoro-1-methylindenyl, and mixture stirs more than 12 hours；So After with water hydrolysis reaction mixture, be dried organic facies and also evaporate solvent, purified, filter, crystallize after obtain 5H-indeno [1,2- B] ligand of pyridine radicals indyl.

The preparation method of synthetic lubricant base oil metallocene poly-alpha olefins catalyst of the present invention, preferably described Step (4) is: be dissolved in ether by halo hexamethylene silane, and drips n-BuLi wherein, then drips metal halide, After stirring the mixture at least 12 hours, or halo substituted benzene is dissolved in ether, and drips n-BuLi wherein, then Dropping metal halide, after stirring the mixture at least 12 hours, adds preparation 5H-indeno [1, the 2-b] pyridine of step (3) Base/2,3,4,5-tetra-fluoro-1-methylindenyl ligand lithium salts, then after including the steps such as extraction, distillation, purification, crystallization Process, i.e. can get product catalyst.

1) substrate is 5H-indeno [1,2-b] thiopyranyl, includes that step (1) preparation replaces ring penta during cyclopentadienyl group Dialkylene；(2) 5H-indeno [1,2-b] thiopyranyl/cyclopentadienyl ligand lithium salts is prepared；(3) halo hexamethylene silicon is prepared Alkyl coordination metal compound, then by the ether of 5H-indeno [1,2-b] thiopyranyl/cyclopentadienyl ligand lithium salts Solution reacts with cyclohexasilanyl coordination metal compound, to obtain corresponding metallocene poly-alpha olefins catalyst.

The preparation method of synthetic lubricant base oil metallocene poly-alpha olefins catalyst of the present invention, the most described step Suddenly (3) are: are dissolved in ether by 5H-indeno [1,2-b] thio-pyrylium and mix with the hexane solution of n-BuLi, then stirring Mix several hours；Add equimolar substituted cyclopentadienyl, and mixture stirs more than 12 hours；Then with water hydrolysis Mixture, is dried organic facies and also evaporates solvent, purified, filter, crystallize after obtain 5H-indeno [1,2-b] thio-pyrylium basic ring The ligand of pentadienyl.

The preparation method of synthetic lubricant base oil metallocene poly-alpha olefins catalyst of the present invention, preferably described Step (4) is: be dissolved in ether by halo hexamethylene silane, and drips n-BuLi wherein, then drips metal halide, After stirring the mixture at least 12 hours, or halo substituted benzene is dissolved in ether, and drips n-BuLi wherein, then Dropping metal halide, after stirring the mixture at least 12 hours, adds preparation 5H-indeno [1, the 2-b] sulfur of step (3) for pyrrole Mutter base/cyclopentadienyl ligand lithium salts, then through including the post processing of the steps such as extraction, distillation, purification, crystallization, To product catalyst.

2) substrate is 5H-indeno [1,2-b] thiopyranyl, includes that step (1) preparation replaces benzo during benzothienyl Thienyl；(2) 5H-indeno [1,2-b] thiopyranyl/benzothienyl ligand lithium salts is prepared；(3) halogenated cyclic silicon is prepared Alkyl coordination metal compound, then by the second of 5H-indeno [1,2-b] thiopyranyl base/benzothienyl ligand lithium salts Ethereal solution reacts with cyclohexasilanyl coordination metal compound, to obtain corresponding metallocene poly-alpha olefins catalyst.

The preparation method of synthetic lubricant base oil metallocene poly-alpha olefins catalyst of the present invention, the most described step Suddenly (3) are: be dissolved in ether by 5H-indeno [1,2-b] thio-pyrylium radical derivative and mixed with the hexane solution of n-BuLi Close, then stir several hours；Add equimolar replacement benzothienyl, and mixture stirs more than 12 hours；Then with Water hydrolysis reaction mixture, is dried organic facies and also evaporates solvent, purified, filter, crystallize after obtain 5H-indeno [1,2-b] sulfur Ligand for pyranose benzothienyl.

The preparation method of synthetic lubricant base oil metallocene poly-alpha olefins catalyst of the present invention, preferably described Step (4) is: be dissolved in ether by halo hexamethylene silane, and drips n-BuLi wherein, then drips metal halide, After stirring the mixture at least 12 hours, or halo substituted benzene is dissolved in ether, and drips n-BuLi wherein, then Dropping metal halide, after stirring the mixture at least 12 hours, adds preparation 5H-indeno [1, the 2-b] sulfur of step (3) for pyrrole Mutter base/benzothienyl ligand lithium salts, then through including the post processing of the steps such as extraction, distillation, purification, crystallization, To product catalyst.

3) substrate is 5H-indeno [1,2-b] thiopyranyl, includes that step (1) prepares substituted indolyl during indyl； (2) preparation replaces 5H-indeno [1,2-b] thiopyranyl/indyl ligand lithium salts；(3) halogenated cyclic silane basigamy is prepared Position metallic compound, then by diethyl ether solution and the hexamethylene of 5H-indeno [1,2-b] thiopyranyl/indyl ligand lithium salts Silylation coordination metal compound reacts, to obtain corresponding metallocene poly-alpha olefins catalyst.

The preparation method of synthetic lubricant base oil metallocene poly-alpha olefins catalyst of the present invention, the most described step Suddenly (3) are: are dissolved in ether by 5H-indeno [1,2-b] thio-pyrylium and mix with the hexane solution of n-BuLi, then stirring Mix several hours；Add equimolar substituted indolyl, and mixture stirs more than 12 hours；Then mix with water hydrolysis Thing, is dried organic facies and also evaporates solvent, purified, filter, crystallize after obtain 5H-indeno [1,2-b] thio-pyrylium indyl Ligand.

The preparation method of synthetic lubricant base oil metallocene poly-alpha olefins catalyst of the present invention, preferably described Step (4) is: be dissolved in ether by halo hexamethylene silane, and drips n-BuLi wherein, then drips metal halide, After stirring the mixture at least 12 hours, or halo substituted benzene is dissolved in ether, and drips n-BuLi wherein, then Dropping metal halide, after stirring the mixture at least 12 hours, adds preparation 5H-indeno [1, the 2-b] sulfur of step (3) for pyrrole Mutter base/indyl ligand lithium salts, then through including the post processing of the steps such as extraction, distillation, purification, crystallization, i.e. can be produced Thing catalyst.

The application of synthetic lubricant base oil metallocene poly-alpha olefins catalyst of the present invention, it is as synthesis profit The catalyst of lubricant base oil reaction, during reaction, its addition is reaction-ure mixture 0.1～10ppm wt%, preferably 0.2ppm Wt%, 0.5ppmwt%, 0.6ppm wt%, 0.8ppm wt%, 1.0ppm wt%, 1.3ppm wt%, 1.5ppm wt%, 1.8ppm wt%, 2.0ppm wt%, 2.3ppm wt%, 2.5ppm wt%, 3.0ppm wt%, 4ppm wt%, 5ppm Wt%, 6ppm wt%, 7ppm wt%, 8ppm wt%, 9ppm wt%, 10ppm wt%.

4) substrate is 5H-indeno [1,2-b] thiopyranyl, includes step (1) during 2,3,4,5-tetra-fluoro-1-methylindenyl The preparation fluoro-1-methylindenyl of replacement 2,3,4,5-tetra-；(2) 5H-indeno [1,2-b] thiopyranyl/2,3,4,5-tetra-fluoro-1-first Base indenyl ligands lithium salts；(3) halogenated cyclic silylation coordination metal compound is prepared, then by 5H-indeno [1,2-b] sulfur generation Pyranose/2, the diethyl ether solution of 3,4,5-tetra-fluoro-1-methylindenyl ligand lithium salts and cyclohexasilanyl coordination metal compound Reaction, to obtain corresponding metallocene poly-alpha olefins catalyst.

The preparation method of synthetic lubricant base oil metallocene poly-alpha olefins catalyst of the present invention, the most described step Suddenly (3) are: be dissolved in ether by 5H-indeno [1,2-b] thio-pyrylium radical derivative and mixed with the hexane solution of n-BuLi Close, then stir several hours；Add equimolar 2,3,4,5-tetra-fluoro-1-methylindenyl, and mixture stir 12 hours with On；Then with water hydrolysis reaction mixture, be dried organic facies and also evaporate solvent, purified, filter, crystallize after obtain 5H-indeno The ligand of [1,2-b] thiopyranyl indyl.

The preparation method of synthetic lubricant base oil metallocene poly-alpha olefins catalyst of the present invention, preferably described Step (4) is: be dissolved in ether by halo hexamethylene silane, and drips n-BuLi wherein, then drips metal halide, After stirring the mixture at least 12 hours, or halo substituted benzene is dissolved in ether, and drips n-BuLi wherein, then Dropping metal halide, after stirring the mixture at least 12 hours, adds preparation 5H-indeno [1, the 2-b] sulfur of step (3) for pyrrole Muttering base/2,3,4,5-tetra-fluoro-1-methylindenyl ligand lithium salts, then through including the steps such as extraction, distillation, purification, crystallization Post processing, i.e. can get product catalyst.

The application of synthetic lubricant base oil metallocene poly-alpha olefins catalyst of the present invention, it is as synthesis profit The catalyst of lubricant base oil reaction, during reaction, its addition is reaction-ure mixture 0.1～10ppm wt%, preferably 0.2ppm Wt%, 0.5ppm wt%, 0.6ppm wt%, 0.8ppm wt%, 1.0ppm wt%, 1.3ppm wt%, 1.5ppm wt%, 1.8ppmwt%, 2.0ppm wt%, 2.3ppm wt%, 2.5ppm wt%, 3.0ppm wt%, 4ppm wt%, 5ppm Wt%, 6ppmwt%, 7ppm wt%, 8ppm wt%, 9ppm wt%, 10ppm wt%.

The preparation method of one-tenth lube base oil metallocene poly-alpha olefins catalyst of the present invention, described step (1) 3 monosubstituted or 3,6-bis-substituted fluorene derivant preparation method is:

One, when substituent group is F, Cl, Br, I, preparation method comprises the steps:

1) from 9-Fluorenone, 9-Fluorenone carries out electrophilic substitution reaction with electrophilic reagent in the presence of a catalyst, obtains 3 Monosubstituted or 3,6 dibasic 9-Fluorenone nitro-derivatives, such as logical formula II；Described electrophilic reagent is nitronium, excellent Selecting nitric acid as the source of nitronium, catalyst is concentrated acid, preferably concentrated sulphuric acid；The usage amount of electrophilic reagent is 9-Fluorenone substrate 1.1-2.5 times mole preferably 1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2.0,2.1,2.2,2.3,2.4, 2.5 times moles, usage amount is 0.1-0.5 times of equivalent of electrophilic reagent, preferably 0.1,0.2,0.3,0.4,0.5 times of equivalent.9-fluorenes Ketone is 1: 25-35: 30-40 with the mol ratio of nitric acid and sulphuric acid

Wherein R2 is nitro or hydrogen atom；

2) monosubstituted or 3 by 3,6 dibasic 9-Fluorenone nitro-derivatives carry out reduction reaction with reducing agent, raw Become 3 monosubstituted or 3,6 dibasic 9-Fluorenone aminoderivatives, such as logical formula (III): as described in reducing agent be zinc powder, copper Powder or iron powder, its usage amount is 1.1-3.0 times of equivalent of 9-Fluorenone nitro-derivative, preferably 1.1,1.2,1.3,1.4,1.5, 1.6,1.7,1.8,1.9,2.0,2.1,2.2,2.3,2.4,2.5,2.6,2.7,2.8,2.9,3.0 equivalent.

Wherein: R2 is nitro or hydrogen atom；

3) this step is divided into 2 kinds of situations, one be substituent group be Cl, Br, I；It two is F for substituent group.

Situation one, the most finally prepares Cl, Br, I substituted 3 monosubstituted or 3, during 6-bis-substituted fluorene derivant: 3 monosubstituted Or 3,6 dibasic 9-Fluorenone aminoderivatives and diazotization agent generation diazo-reaction, generate 3 monosubstituted or 3, 6 dibasic 9-Fluorenone diazo derivants, such as logical formula (IV), described diazotization agent is sodium nitrite or potassium nitrite, its Addition be corresponding 3 monosubstituted or 3,1.1-1.5 times of equivalent of 6 dibasic 9-Fluorenone aminoderivatives, preferably 1.1,1.2,1.3,1.4,1.5 times of equivalents.

Wherein R₂For diazonium cation or hydrogen atom；

3 generated monosubstituted or 3, and 6 dibasic 9-Fluorenone diazo derivants are reacted with nucleopilic reagent again, quilt Nucleophilic group replaces, generate corresponding 3 monosubstituted or 3,6 dibasic 9-Fluorenone derivants (V), described nucleopilic reagent For cuprous bromide, its addition is the 1.1-2.5 equivalent of corresponding diazol, preferably 1.1,1.2,1.3,1.4,1.5,1.6,1.7, 1.8,1.9,2.0,2.1,2.2,2.3,2.4,2.5 equivalent.

Wherein: R₁For Cl, Br, I, R₂For H, Cl, Br, I；

Situation two, the most finally prepares F substituted 3 monosubstituted or 3, during 6-bis-substituted fluorene derivant: 3 are monosubstituted or 3, 6 dibasic 9-Fluorenone aminoderivatives and diazotization agent, fluoboric acid generation diazo-reaction, generate 3 monosubstituted or 3,6 dibasic 9-Fluorenone NITRODIAZONIUM FLUOROBORATEs, such as structural formula (VII), then through Pintsch process obtain 3 monosubstituted or 3,6 The dibasic 9-Fluorenone derivant in position；

4) 3 monosubstituted or 3,6 dibasic 9-Fluorenone derivants with go back original reagent through reduction reaction, available Corresponding 3 replacements or 3,6 dibasic 9-fluorene derivatives (VI), described in go back original reagent be zinc amalgam, its addition is corresponding The 1.1-2.5 equivalent of 9-Fluorenone derivant, preferably 1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2.0,2.1, 2.2、2.3、2.4、2.5。

Wherein: R₁For F, R₂For H or F.

Two, aforesaid 3 monosubstituted or 3, the preparation method of 6-bis-substituted fluorene derivant, wherein substituent group carbochain be 2-24 i.e. 2, the direct-connected or branched paraffin of 3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24 Preparation method in a period of time, including abovementioned steps 1), 2), 3), 4), also include step 5).Step 5) be

By step 4) product is dissolved in solvent, and add magnesium powder and the iodine of catalytic amount, after reaction completely, drip aqueous ammonium chloride solution Cancellation is reacted, then obtains end product after drying, crystallization.

The present invention has positive effect: synthetic lubricant base oil metallocene poly alpha olefin disclosed by the invention is catalyzed Agent mPAO with disclosed in existing compares, and advantage is Stability Analysis of Structures, and catalytic efficiency is high.The preparation method of the present invention is easy and simple to handle, product Rate is high, raw material is easy to get, and low cost, environmental pollution are little, it is easy to industrialized production.

Detailed description of the invention

(embodiment 1) 3-fluorine substituted fluorene is the zirconium metal catalyzer of part carbon bridging

(1) synthesis of 3-fluorine substituted fluorene.

Joining in reactor by 9-Fluorenone (1.8g, 10mmol) and water (70mL), stirring, heating, when temperature rises to 80- Start to drip 108 grams of the mixed acid (nitric acid and sulphuric acid 4:7 mixing) of nitric acid and sulphuric acid when 90 DEG C, react 2.5-4h under backflow, add Shrend is gone out reaction, sucking filtration, and gained solids with methanol and glacial acetic acid are recrystallized to give 3-nitro-9-Fluorenone (1.87g, 83% receives Rate).Feature:¹H NMR(CHCl₃d³) δ ppm:8.44 (m, 1H, aromatic ring H) 8.34 (m, 1H, aromatic ring H), 8.22 (s, 1H, aromatic rings H), 7.70 (m, 1H, aromatic ring H), 7.51 (m, 1H, aromatic ring H), 7.24 (d, 1H, aromatic ring H), 7.05 (d, 1H, aromatic ring H).

3-nitro-9-Fluorenone (1.87g) and ethanol are joined in reactor by weight 1: 50, adds iron powder (465mg) stirring, is heated to reflux, and overnight, TLC detection raw material nitro compound fluorenes has disappeared in reaction.Cooling, is filtered to remove solid Body, is evaporated solution.Adding ethyl acetate 100mL to dissolve, organic facies saturated aqueous common salt 100mL washes 3 times, merges organic facies, dry Drying prescription filters after drying and is evaporated.It is yellowish that ethyl acetate petroleum ether recrystallization i.e. can get the purity 3-amino 9-Fluorenone more than 97% Color solid (1.54g, 95%).Feature:¹H NMR(CHCl₃d³) δ ppm:8.44 (m, 1H, aromatic ring H) 8.34 (m, 1H, aromatic ring H), 7.70 (m, 1H, aromatic ring H), 7.59 (m, 1H, aromatic ring H), 7.51 (m, 1H, aromatic ring H), 6.99 (s, 1H, aromatic ring H), 6.42 (m, 1H, aromatic ring H), 6.27 (m, 2H, NH₂)。

It is cooled to 0～5 DEG C after being mixed by 3-amino 9-Fluorenone (1.54g) and 37% concentrated hydrochloric acid 50mL, adds while stirring 35% sodium nitrite in aqueous solution 30mL, maintains the temperature at and reacts 1～1.5 hour between 0～5 DEG C.Then 40% it is slowly added dropwise Fluoboric acid 20mL, during dropping, viscosity increases, and filters, be filtered dry, then dry after dropping after stirring 15min.Will Diazonium fluoride borate is put in another four-hole bottle being dried, and carries out cracking reaction, is slowly heated, starts, at 50V, white cigarette of emerging After, remove electric jacket, again heat after waiting mitigation, temperature is the longest in about the 130V response time, finally heated to 200 DEG C until Steam without grease, then use steam distillation instead.Separating oil reservoir, water layer 30ml toluene extracts 2 times, merges organic layer, decompression Distillation is until solvent-free steaming, and the weight/mass percentage composition recording the fluoro-9-Fluorenone of 3-through gas chromatogram area normalization method is 99.6%, Yield reaches 80.5%.Product is 3-fluoro-9-Fluorenone 1.25g.Feature:¹H NMR(CHCl₃d³) δ ppm:8.44 (m, 1H, aromatic ring H) 8.34 (m, 1H, aromatic ring H), 7.82 (m, 1H, aromatic ring H), 7.70 (m, 1H, aromatic ring H), 7.62 (m, 1H, aromatic ring H), 7.51 (m, 1H, aromatic ring H), 7.30 (s, 1H, aromatic ring H).

By 615mg zinc powder, 300mg mercuric chloride, 10ml concentrated hydrochloric acid and 40ml water mix and blend 5min, stand.Incline the liquid that anhydrates, Add 40ml 95% ethanol, add the fluoro-9-Fluorenone of 1.25g 3-, back flow reaction 8h, course of reaction is dividedly in some parts the dense salt of 30ml Acid, after hardening, cooling, sucking filtration, crude product ethyl alcohol recrystallization, dried white solid product 3-fluorine substituted fluorene 0.93g.Feature:¹H NMR(CHCl₃d³) δ ppm:7.55 (m, 3H, aromatic ring H) 7.87 (m, 1H, aromatic ring H), 7.38 (m, 2H, aromatic rings H), 6.99 (m, 1H, aromatic ring H), 4.12 (m, 2H, CH₂)。

(2) synthesis of 2-fluorine cyclopentadienyl group: 10mmol sodium bits are added in 10ml ethanol.Then the first of 10mmol is added Benzophenone.Then dropping 20mmol 2-fluorine cyclopentadiene, mixture stirs 15 hours under reflux.The product obtained is then with water Dilute and with extraction into heptane, evaporate organic facies, after the 2-fluorine cyclopentadienyl group of excess is removed in distillation, after being extracted with ethyl acetate, Being dried, filtration is evaporated.

(3) 10mmol 3-fluorine fluorenes is dissolved in 50ml ether and mixes with the 1.6M hexane solution of 10mmol n-BuLi, Then several hours are stirred.Add equimolar replacement 2-fluorine cyclopentadiene, and mixture is stirred overnight.Then with 50ml water water Solve reactant mixture, be dried organic facies with sodium sulfate and evaporate solvent under vacuo, standby.

(4) the 1 of 20mmol, 3,5-trifluoro-benzenes are dissolved in 50mL ether, are cooled to-78 DEG C, the butyl lithium of dropping 20mmol, Adding the Zirconium tetrachloride. of 1eq after adding, go back after mixture is stirred overnight, dropping 10mmol ligand is dissolved in 30ml ether Mixed liquor.After dropping, mixture is stirred overnight, and then evaporates solvent and with dichloromethane extracted residues, merges organic Phase, dried over sodium sulfate, filter and evaporate solvent the most under vacuo.For purification, residue is dissolved in pentane, solution warp Silica gel filters and i.e. can get corresponding 3-fluorine fluorenes-2-fluorine cyclopentadiene-two-1,3,5-trifluorophenyls-dichloro-30 DEG C of crystallizations Change zirconium.Feature:¹H NMR(DMSO d⁶) δ ppm:7.87 (m, 1H, aromatic ring H) 7.55 (m, 3H, aromatic ring H), 7.38 (m, 1H, aromatic rings H), 7.28 (m, 1H, aromatic ring H), 6.99 (m, 1H, aromatic ring H), 6.40 (m, 4H, aromatic ring H), 6.21 (m, 1H, cyclopentadiene H), 6.10 (m, 1H, cyclopentadiene H), 4.66 (m, 2H, aromatic ring H), 2.90 (m, 2H, cyclopentadiene H).

(embodiment 2) 3,6-difluoro substituted fluorene is the zirconium metal catalyzer of part carbon bridging

(1) synthesis of 3,6-difluoro substituted fluorene.

Joining in reactor by 9-Fluorenone (1.8g, 10mmol) and water by weight 1: 7, stirring, heating, when temperature liter Starting to drip 108 grams of the mixed acid (nitric acid and sulphuric acid 8:2 mixing) of nitric acid and sulphuric acid during to 80-90 DEG C, the lower reaction 20 of backflow is little Time, the cancellation that adds water react, sucking filtration, gained solids with methanol and glacial acetic acid recrystallization, be dried 3,6-dinitro-9-Fluorenone (1.35g, 50%).Feature:¹H NMR(CHCl₃d³) δ ppm:8.75 (s, 2H, aromatic ring H) 8.32 (d, 2H, aromatic ring H), 8.10 (d, 2H, aromatic ring H).

By 3,6 dinitros-9-Fluorenone (1.35g) and ethanol join in reactor by weight 1: 5, add iron powder (2mmol) stirring, is heated to reflux, and overnight, TLC detection raw material nitro compound fluorenes has disappeared in reaction.Cooling, is filtered to remove solid Body, is evaporated solution.Adding ethyl acetate 100mL to dissolve, organic facies saturated aqueous common salt 100mL washes 3 times, merges organic facies, dry Drying prescription filters after drying and is evaporated.Ethyl acetate petroleum ether recrystallization i.e. can get purity 3 more than 97%, 6-diaminourea 9-Fluorenone Faint yellow solid (0.95g, 90%).Feature:¹H NMR(CHCl₃d³) δ ppm:7.59 (d, 2H, aromatic ring H), 6.99 (d, 2H, virtues Ring H), 6.42 (d, 2H, aromatic ring H), 6.27 (m, 4H, NH₂)。

By 3, it is cooled to 0～5 DEG C after 6-diaminourea 9-Fluorenone (950mg) and the mixing of 37% concentrated hydrochloric acid, adds while stirring 35% sodium nitrite in aqueous solution, maintains the temperature at and reacts 1～1.5 hour between 0～5 DEG C.Then the fluorine boron of 40% it is slowly added dropwise Acid, during dropping, viscosity increases, and filters, be filtered dry, then dry after dropping after stirring 15min.By diazonium fluoride boron Hydrochlorate is put in another four-hole bottle being dried, and carries out cracking reaction, is slowly heated, start, at 50V, Bai Yanhou of emerging, removes electricity Hot jacket, heats after waiting mitigation again, and temperature is the longest in about the 130V response time, finally heated to 200 DEG C until without grease Steam, then use steam distillation instead.Separate oil reservoir, water layer with 30ml toluene extract 2 times, merge organic layer, decompression distillation until Solvent-free steaming, record 3 through gas chromatogram area normalization method, the weight/mass percentage composition of the fluoro-9-Fluorenone of 6-bis-is 99.6%, yield Reach 80.5%.Product is 3, the fluoro-9-Fluorenone of 6-bis-(700mg, 72%).Feature:¹H NMR(CHCl₃d³)δppm:7.82(m,2H, Aromatic ring H), 7.62 (m, 2H, aromatic ring H), 7.30 (d, 2H, aromatic ring H).

By 3.15g zinc powder, 1.5g mercuric chloride, 10ml concentrated hydrochloric acid and 20ml water mix and blend 5min, stand.Incline the liquid that anhydrates, Add 20ml 95% ethanol, add the fluoro-9-Fluorenone of 700mg 3,6-bis-, back flow reaction 8h, course of reaction is dividedly in some parts 15ml Concentrated hydrochloric acid, after hardening, cooling, sucking filtration, crude product ethyl alcohol recrystallization, dried white solid product 3,6-difluoro takes For fluorenes 523mg.Feature:¹H NMR(CHCl₃d³) δ ppm:7.55 (s, 2H, aromatic ring H), 7.53 (m, 2H, aromatic ring H), 6.99 (d, 2H, aromatic ring H), 4.12 (m, 2H, CH₂)。

(2) synthesis of 2-fluorine cyclopentadienyl group, with embodiment 1 step (2).

(3) 10mmol 3,6-difluoro fluorenes be dissolved in 50ml ether and with the 1.6M hexane solution of 10mmol n-BuLi Mixing, then stirs several hours.Add equimolar 2-fluorine cyclopentadienyl group (ibid) and mixture is stirred overnight.Then with 50ml water hydrolysis reaction mixture, is dried organic facies with sodium sulfate and evaporates solvent under vacuo, standby.

(4) the 1 of 20mmol, 3,5-trifluoro-benzenes are dissolved in 50mL ether, are cooled to-78 DEG C, the butyl lithium of dropping 20mmol, Adding the Zirconium tetrachloride. of 1eq after adding, go back after mixture is stirred overnight, dropping 10mmol ligand is dissolved in 30ml ether Mixed liquor.After dropping, mixture is stirred overnight, and then evaporates solvent and with dichloromethane extracted residues, merges organic Phase, dried over sodium sulfate, filter and evaporate solvent the most under vacuo.For purification, residue is dissolved in pentane, solution warp Silica gel filters and i.e. can get corresponding 3-30 DEG C of crystallizations, and 6-difluoro fluorenes-2-fluorine cyclopentadiene-two-1,3,5-trifluorophenyl- Zirconium dichloride.Feature:¹H NMR(DMSO d⁶) δ ppm:7.55 (m, 4H, aromatic ring H), 7.28 (m, 1H, aromatic ring H), 6.99 (m, 2H, Aromatic ring H), 6.40 (m, 4H, aromatic ring H), 6.21 (m, 1H, cyclopentadiene H), 6.10 (m, 1H, cyclopentadiene H), 4.66 (m, 2H, Aromatic ring H), 2.90 (m, 2H, cyclopentadiene H).

(embodiment 3) 3-ethyl substituted fluorene is the zirconium metal catalyzer of part carbon bridging

(1) synthesis of 3-ethyl substituted fluorene.

Joining in reactor by 9-Fluorenone (1.8g, 10mmol) and water by weight 1: 7, stirring, heating, when temperature liter Starting to drip 108 grams of the mixed acid (nitric acid and sulphuric acid 8:2 mixing) of nitric acid and sulphuric acid during to 80-90 DEG C, the lower reaction 20 of backflow is little Time, the cancellation that adds water react, sucking filtration, gained solids with methanol and glacial acetic acid recrystallization, be dried 3-nitro-9-Fluorenone (1.35g, 50%).Feature:¹H NMR(CHCl₃d³) δ ppm:8.75 (s, 1H, aromatic ring H) 8.44 (m, 1H, aromatic ring H), 8.34 (m, 1H, aromatic rings H), 8.32 (d, 1H, aromatic ring H) 8.10 (d, 1H, aromatic ring H), 7.70 (m, 1H, aromatic ring H), 7.51 (m, 1H, aromatic ring H).

3-nitro-9-Fluorenone (1.35g) and ethanol are joined in reactor by weight 1: 5, adds iron powder (2mmol) Stirring, is heated to reflux, and overnight, TLC detection raw material nitro compound fluorenes has disappeared in reaction.Cooling, solids removed by filtration, it is evaporated Solution.Adding ethyl acetate 100mL to dissolve, organic facies saturated aqueous common salt 100mL washes 3 times, merges organic facies, desiccant dryness Rear filtration is evaporated.Ethyl acetate petroleum ether recrystallization i.e. can get the purity 3-amino 9-Fluorenone faint yellow solid more than 97% (0.95g, 90%).Feature:¹H NMR(CHCl₃d³) δ ppm:8.44 (m, 1H, aromatic ring H) 8.34 (m, 1H, aromatic ring H), 7.70 (m, 1H, aromatic ring H), 7.59 (m, 1H, aromatic ring H), 7.51 (m, 1H, aromatic ring H), 6.99 (s, 1H, aromatic ring H), 6.42 (m, 1H, aromatic rings H),6.27(m,2H,NH₂)。

It is cooled to 0～5 DEG C after 3-amino 9-Fluorenone (1.95g) and 37% concentrated hydrochloric acid being mixed, adds 35% while stirring Sodium nitrite in aqueous solution, maintains the temperature at and reacts 1～1.5 hour between O～5 DEG C.Then it is slowly added dropwise hydrobromic acid, drips complete The protobromide ketone of rear addition catalytic amount, is warming up to 50 DEG C again and reacts two hours after being warming up to room temperature.TLC display reaction is complete. Stopped reaction.Solids removed by filtration.Add ethyl acetate extraction 100mL to carry out extracting 3 times.Merge organic facies.Desiccant dryness After, it is filtered to remove desiccant.It is evaporated.Thick product ethyl acetate and petroleum ether carry out recrystallization and can obtain the bromo-9-Fluorenone of white 3- Solid (2.33g, 90%).Feature:¹H NMR(CHCl₃d³) δ ppm:8.44 (m, 1H, aromatic ring H) 8.34 (m, 1H, aromatic ring H), 8.22 (s, 1H, aromatic ring H), 7.70 (m, 1H, aromatic ring H), 7.51 (m, 1H, aromatic ring H), 7.24 (d, 1H, aromatic ring H), 7.05 (d, 1H, aromatic ring H).

By 877mg zinc powder, 405mg mercuric chloride, 20ml concentrated hydrochloric acid and 40ml water mix and blend 5min, stand.Incline the liquid that anhydrates, Add 40ml 95% ethanol, add the bromo-9-Fluorenone of 2.33g 3-, back flow reaction 8h, course of reaction is dividedly in some parts the dense salt of 30ml Acid, after hardening, cooling, sucking filtration, crude product ethyl alcohol recrystallization, dried white solid product 3-bromine substituted fluorene 1.87g, productivity 85%.Feature:¹H NMR(CHCl₃d³) δ ppm:8.01 (s, 1H, aromatic ring H) 7.87 (m, 1H, aromatic ring H), 7.55 (s, 1H, aromatic ring H), 7.45 (m, 2H, aromatic ring H), 7.38 (m, 1H, aromatic ring H), 7.28 (m, 1H, aromatic ring H), 4.12 (m, 2H, CH₂)。

3-bromine fluorenes solid (1.87g) is dissolved in 50 milliliters of anhydrous tetrahydro furans, adds the magnesium powder 200mg of 1.1 equivalents and urge The iodine of change amount, heats up, and after reaction initiation, continuation reacting by heating is after 2 hours, and cooling, the oxolane being filtrated to get grignard reagent is molten Liquid.It is cooled to interior temperature 0 DEG C-5 DEG C, then drips the solution of bromic ether.Room temperature reaction it is warming up to again 4 hours after dropping.TLC Display reaction is the most complete.Slowly dropping aqueous ammonium chloride solution cancellation reaction.Extract 3 times by 25 milliliters of ethyl acetate, be associated with Machine phase.After organic facies desiccant dryness, it is filtered to remove desiccant.Solvent evaporated.Thick product ethyl acetate and petroleum ether weight Crystallization.I.e. available white 3-ethyl fluorenes solid (889mg, 60%).Feature:¹H NMR(CHCl₃d³)δppm:7.87(s,1H, Aromatic ring H) 7.10 (m, 1H, aromatic ring H), 7.55 (s, 1H, aromatic ring H), 7.50 (m, 1H, aromatic ring H), 7.38 (m, 1H, aromatic ring H), 7.28 (m, 1H, aromatic ring H), 7.14 (m, 1H, aromatic ring H), 4.12 (m, 2H, CH₂),2.60(m,2H,CH₂),1.25(t,3H, CH₃)。

(2) with embodiment 1 step (2)

(3) 10mmol 3-ethyl fluorenes is dissolved in 50ml ether and mixed with the 1.6M hexane solution of 10mmol n-BuLi Close, then stir several hours.Add equimolar replacement 2-fluorine cyclopentadiene, and mixture is stirred overnight.Then with 50ml Water hydrolysis reaction mixture, is dried organic facies with sodium sulfate and evaporates solvent under vacuo, standby.

(4) the 1 of 20mmol, 3,5-trifluoro-benzenes are dissolved in 50mL ether, are cooled to-78 DEG C, the butyl lithium of dropping 20mmol, Adding the Zirconium tetrachloride. of 1eq after adding, go back after mixture is stirred overnight, dropping 10mmol ligand is dissolved in 30ml ether Mixed liquor.After dropping, mixture is stirred overnight, and then evaporates solvent and with dichloromethane extracted residues, merges organic Phase, dried over sodium sulfate, filter and evaporate solvent the most under vacuo.For purification, residue is dissolved in pentane, solution warp Silica gel filters and i.e. can get corresponding 3-ethyl fluorenes-2-fluorine cyclopentadiene-two-1,3,5-trifluorophenyl-two-30 DEG C of crystallizations Zirconium chloride.Feature:¹H NMR(DMSO d⁶) δ ppm:7.55 (m, 4H, aromatic ring H), 7.28 (m, 1H, aromatic ring H), 6.99 (m, 2H, virtue Ring H), 6.40 (m, 4H, aromatic ring H), 6.21 (m, 1H, cyclopentadiene H), 6.10 (m, 1H, cyclopentadiene H), 4.66 (m, 2H, virtues Ring H), 2.90 (m, 2H, cyclopentadiene H), 2.60 (m, 2H, CH₂),1.25(m,3H,CH₃)。

(embodiment 4) 3-fluorine substituted fluorene is the titanium catalyst of part carbon bridging

(1) synthesis of 3-fluorine substituted fluorene, with embodiment 1 step (1).

(4) the 1 of 20mmol, 3,5-trifluoro-benzenes are dissolved in 50mL ether, are cooled to-78 DEG C, the butyl lithium of dropping 20mmol, Adding the titanium tetrachloride of 1eq after adding, go back after mixture is stirred overnight, dropping 10mmol ligand is dissolved in 30ml ether Mixed liquor.After dropping, mixture is stirred overnight, and then evaporates solvent and with dichloromethane extracted residues, merges organic Phase, dried over sodium sulfate, filter and evaporate solvent the most under vacuo.For purification, residue is dissolved in pentane, solution warp Silica gel filters and i.e. can get corresponding 3-fluorine fluorenes-2-fluorine cyclopentadiene-two-1,3,5-trifluorophenyls-dichloro-30 DEG C of crystallizations Change titanium.Feature:¹H NMR(DMSO d⁶) δ ppm:7.87 (m, 1H, aromatic ring H) 7.55 (m, 3H, aromatic ring H), 7.38 (m, 1H, aromatic rings H), 7.28 (m, 1H, aromatic ring H), 6.99 (m, 1H, aromatic ring H), 6.40 (m, 4H, aromatic ring H), 6.21 (m, 1H, cyclopentadiene H), 6.10 (m, 1H, cyclopentadiene H), 4.66 (m, 2H, aromatic ring H), 2.90 (m, 2H, cyclopentadiene H).

(embodiment 5) 3,6-difluoro substituted fluorene is the titanium catalyst of part carbon bridging

The synthesis of (1) 3,6-difluoro substituted fluorene, with embodiment 2 step (1).

(2) synthesis of 2-fluorine cyclopentadienyl group, with the step (2) of embodiment 4.

(4) the 1 of 20mmol, 3,5-trifluoro-benzenes are dissolved in 50mL ether, are cooled to-78 DEG C, the butyl lithium of dropping 20mmol, Adding the titanium tetrachloride of 1eq after adding, go back after mixture is stirred overnight, dropping 10mmol ligand is dissolved in 30ml ether Mixed liquor.After dropping, mixture is stirred overnight, and then evaporates solvent and with dichloromethane extracted residues, merges organic Phase, dried over sodium sulfate, filter and evaporate solvent the most under vacuo.For purification, residue is dissolved in pentane, solution warp Silica gel filters and i.e. can get corresponding 3-30 DEG C of crystallizations, and 6-difluoro fluorenes-2-fluorine cyclopentadiene-two-1,3,5-trifluorophenyl- Titanium chloride.Feature:¹H NMR(DMSO d⁶) δ ppm:7.55 (m, 4H, aromatic ring H), 7.28 (m, 1H, aromatic ring H), 6.99 (m, 2H, Aromatic ring H), 6.40 (m, 4H, aromatic ring H), 6.21 (m, 1H, cyclopentadiene H), 6.10 (m, 1H, cyclopentadiene H), 4.66 (m, 2H, Aromatic ring H), 2.90 (m, 2H, cyclopentadiene H).

(embodiment 6) 3-ethyl substituted fluorene is the titanium catalyst of part carbon bridging

(1) 3-ethyl substituted fluorene, with embodiment 3 step (1).

(4) the 1 of 20mmol, 3,5-trifluoro-benzenes are dissolved in 50mL ether, are cooled to-78 DEG C, the butyl lithium of dropping 20mmol, Adding the titanium tetrachloride of 1eq after adding, go back after mixture is stirred overnight, dropping 10mmol ligand is dissolved in 30ml ether Mixed liquor.After dropping, mixture is stirred overnight, and then evaporates solvent and with dichloromethane extracted residues, merges organic Phase, dried over sodium sulfate, filter and evaporate solvent the most under vacuo.For purification, residue is dissolved in pentane, solution warp Silica gel filters and i.e. can get corresponding 3-ethyl fluorenes-2-fluorine cyclopentadiene-two-1,3,5-trifluorophenyl-two-30 DEG C of crystallizations Titanium chloride.Feature:¹H NMR(DMSO d⁶) δ ppm:7.55 (m, 4H, aromatic ring H), 7.28 (m, 1H, aromatic ring H), 6.99 (m, 2H, virtue Ring H), 6.40 (m, 4H, aromatic ring H), 6.21 (m, 1H, cyclopentadiene H), 6.10 (m, 1H, cyclopentadiene H), 4.66 (m, 2H, virtues Ring H), 2.90 (m, 2H, cyclopentadiene H), 2.60 (m, 2H, CH₂),1.25(m,3H,CH₃)。

(embodiment 7) 3-fluorine substituted fluorene is the hafnium metallic catalyst of part carbon bridging

(1) synthesis of 3-fluorine substituted fluorene, with embodiment 1 step (1).

(4) the 1 of 20mmol, 3,5-trifluoro-benzenes are dissolved in 50mL ether, are cooled to-78 DEG C, the butyl lithium of dropping 20mmol, Adding the hafnium tetrachloride of 1eq after adding, go back after mixture is stirred overnight, dropping 10mmol ligand is dissolved in 30ml ether Mixed liquor.After dropping, mixture is stirred overnight, and then evaporates solvent and with dichloromethane extracted residues, merges organic Phase, dried over sodium sulfate, filter and evaporate solvent the most under vacuo.For purification, residue is dissolved in pentane, solution warp Silica gel filters and i.e. can get corresponding 3-fluorine fluorenes-2-fluorine cyclopentadiene-two-1,3,5-trifluorophenyl-two-30 DEG C of crystallizations Hafnium chloride.Feature:¹H NMR(DMSO d⁶) δ ppm:7.87 (m, 1H, aromatic ring H) 7.55 (m, 3H, aromatic ring H), 7.38 (m, 1H, virtues Ring H), 7.28 (m, 1H, aromatic ring H), 6.99 (m, 1H, aromatic ring H), 6.40 (m, 4H, aromatic ring H), 6.21 (m, 1H, cyclopentadiene H), 6.10 (m, 1H, cyclopentadiene H), 4.66 (m, 2H, aromatic ring H), 2.90 (m, 2H, cyclopentadiene H).

(embodiment 8) 3,6-difluoro substituted fluorene is the hafnium metallic catalyst of part carbon bridging

(4) the 1 of 20mmol, 3,5-trifluoro-benzenes are dissolved in 50mL ether, are cooled to-78 DEG C, the butyl lithium of dropping 20mmol, Adding the hafnium tetrachloride of 1eq after adding, go back after mixture is stirred overnight, dropping 10mmol ligand is dissolved in 30ml ether Mixed liquor.After dropping, mixture is stirred overnight, and then evaporates solvent and with dichloromethane extracted residues, merges organic Phase, dried over sodium sulfate, filter and evaporate solvent the most under vacuo.For purification, residue is dissolved in pentane, solution warp Silica gel filters and i.e. can get corresponding 3-30 DEG C of crystallizations, and 6-difluoro fluorenes-2-fluorine cyclopentadiene-two-1,3,5-trifluorophenyl- Hafnium dichloride.Feature:¹H NMR(DMSO d⁶) δ ppm:7.55 (m, 4H, aromatic ring H), 7.28 (m, 1H, aromatic ring H), 6.99 (m, 2H, Aromatic ring H), 6.40 (m, 4H, aromatic ring H), 6.21 (m, 1H, cyclopentadiene H), 6.10 (m, 1H, cyclopentadiene H), 4.66 (m, 2H, Aromatic ring H), 2.90 (m, 2H, cyclopentadiene H).

(embodiment 9) 3-ethyl substituted fluorene is the hafnium metallic catalyst of part carbon bridging

(1) 3-ethyl substituted fluorene, with embodiment 3 step (1).

(4) the 1 of 20mmol, 3,5-trifluoro-benzenes are dissolved in 50mL ether, are cooled to-78 DEG C, the butyl lithium of dropping 20mmol, Adding the hafnium tetrachloride of 1eq after adding, go back after mixture is stirred overnight, dropping 10mmol ligand is dissolved in 30ml ether Mixed liquor.After dropping, mixture is stirred overnight, and then evaporates solvent and with dichloromethane extracted residues, merges organic Phase, dried over sodium sulfate, filter and evaporate solvent the most under vacuo.For purification, residue is dissolved in pentane, solution warp Silica gel filters and i.e. can get corresponding 3-ethyl fluorenes-2-fluorine cyclopentadiene-two-1,3,5-trifluorophenyl-two-30 DEG C of crystallizations Hafnium chloride.Feature:¹H NMR(DMSO d⁶) δ ppm:7.55 (m, 4H, aromatic ring H), 7.28 (m, 1H, aromatic ring H), 6.99 (m, 2H, virtue Ring H), 6.40 (m, 4H, aromatic ring H), 6.21 (m, 1H, cyclopentadiene H), 6.10 (m, 1H, cyclopentadiene H), 4.66 (m, 2H, virtues Ring H), 2.90 (m, 2H, cyclopentadiene H), 2.60 (m, 2H, CH₂),1.25(m,3H,CH₃)。

(embodiment 10) 3-fluorine substituted fluorene is part silicon bridge zirconium metal catalyzer even

(1) synthesis of 3-fluorine substituted fluorene.With example 1 step (1)

(2) synthesis of 2-fluorine cyclopentadienyl group: with example 1 step (2)

(4) the cyclohexyl methyl chlorosilane of 20mmol is dissolved in 50mL ether, is cooled to-78 DEG C, the fourth of dropping 20mmol Base lithium, adds the Zirconium tetrachloride. of 1eq after adding, go back after mixture is stirred overnight, and dropping 10mmol ligand is dissolved in 30ml second Mixed liquor in ether.After dropping, mixture is stirred overnight, and then evaporates solvent and with dichloromethane extracted residues, closes And organic facies, dried over sodium sulfate, filter and evaporate solvent the most under vacuo.For purification, residue is dissolved in pentane, Solution filters through silica gel and i.e. can get corresponding 3-fluorine fluorenes-2-fluorine cyclopentadiene-cyclohexyl methyl silicon-two-30 DEG C of crystallizations Zirconium chloride.Feature:¹H NMR(DMSO d⁶) δ ppm:7.87 (m, 1H, aromatic ring H) 7.55 (m, 3H, aromatic ring H), 7.38 (m, 1H, virtues Ring H), 7.28 (m, 1H, aromatic ring H), 6.99 (m, 1H, aromatic ring H), 6.21 (m, 1H, cyclopentadiene H), 6.10 (m, 1H, rings penta 2 Alkene H), 4.66 (m, 2H, aromatic ring H), 2.90 (m, 2H, cyclopentadiene H), 0.85 (m, 10H, cyclohexyl H).

(embodiment 11) 3,6-difluoro substituted fluorene is part silicon bridge zirconium metal catalyzer even

(1) synthesis of 3,6-difluoro substituted fluorene.With embodiment 1 step (1)

(2) synthesis of 2-fluorine cyclopentadienyl group, with embodiment 1 step (2).

(4) the cyclohexyl chloride silane of 20mmol is dissolved in 50mL ether, is cooled to-78 DEG C, the butyl lithium of dropping 20mmol, Adding the Zirconium tetrachloride. of 1eq after adding, go back after mixture is stirred overnight, dropping 10mmol ligand is dissolved in 30ml ether Mixed liquor.After dropping, mixture is stirred overnight, and then evaporates solvent and with dichloromethane extracted residues, merges organic Phase, dried over sodium sulfate, filter and evaporate solvent the most under vacuo.For purification, residue is dissolved in pentane, solution warp Silica gel filters and also i.e. can get corresponding 3-30 DEG C of crystallizations, and 6-difluoro fluorenes-2-fluorine cyclopentadiene-cyclohexyl is silica-based-dichloride Zirconium.Feature:¹H NMR(DMSO d⁶) δ ppm:7.55 (m, 4H, aromatic ring H), 7.28 (m, 1H, aromatic ring H), 6.99 (m, 2H, aromatic rings H), 6.21 (m, 1H, cyclopentadiene H), 6.10 (m, 1H, cyclopentadiene H), 4.66 (m, 2H, aromatic ring H), 2.90 (m, 2H, rings penta Diene H), 0.85 (m, 10H, cyclohexyl H).

(embodiment 12) 3-ethyl substituted fluorene is part silicon bridge zirconium metal catalyzer even

(1) synthesis of 3-ethyl substituted fluorene.With embodiment 1

(2) with embodiment 1 step (2)

(4) being dissolved in 50mL ether of 20mmol cyclohexyl chloride silane, is cooled to-78 DEG C, the butyl lithium of dropping 20mmol, Adding the Zirconium tetrachloride. of 1eq after adding, go back after mixture is stirred overnight, dropping 10mmol ligand is dissolved in 30ml ether Mixed liquor.After dropping, mixture is stirred overnight, and then evaporates solvent and with dichloromethane extracted residues, merges organic Phase, dried over sodium sulfate, filter and evaporate solvent the most under vacuo.For purification, residue is dissolved in pentane, solution warp Silica gel filter and-30 DEG C crystallization i.e. can get corresponding 3-ethyl fluorenes-2-fluorine cyclopentadiene-cyclohexyl silica-based-zirconium dichloride. Feature:¹H NMR(DMSO d⁶) δ ppm:7.55 (m, 4H, aromatic ring H), 7.28 (m, 1H, aromatic ring H), 6.99 (m, 2H, aromatic ring H), 6.21 (m, 1H, cyclopentadiene H), 6.10 (m, 1H, cyclopentadiene H), 4.66 (m, 2H, aromatic ring H), 2.90 (m, 2H, cyclopentadiene H),2.60(m,2H,CH₂),1.25(m,3H,CH₃), 0.85 (m, 10H, cyclohexyl H).

(embodiment 13) 3-fluorine substituted fluorene is part silicon bridge titanium catalyst even

(1) synthesis of 3-fluorine substituted fluorene, with embodiment 1 step (1).

(2) synthesis of 2-fluorine cyclopentadienyl group: with embodiment 1 step (2).

(4) the cyclohexyl chloride silane of 20mmol is dissolved in 50mL ether, is cooled to-78 DEG C, the butyl lithium of dropping 20mmol, Adding the titanium tetrachloride of 1eq after adding, go back after mixture is stirred overnight, dropping 10mmol ligand is dissolved in 30ml ether Mixed liquor.After dropping, mixture is stirred overnight, and then evaporates solvent and with dichloromethane extracted residues, merges organic Phase, dried over sodium sulfate, filter and evaporate solvent the most under vacuo.For purification, residue is dissolved in pentane, solution warp Silica gel filter and-30 DEG C crystallization i.e. can get corresponding 3-fluorine fluorenes-2-fluorine cyclopentadiene-cyclohexyl chloride silica-based-titanium chloride. Feature:¹H NMR(DMSO d⁶) δ ppm:7.87 (m, 1H, aromatic ring H) 7.55 (m, 3H, aromatic ring H), 7.38 (m, 1H, aromatic ring H), (7.28 m, 1H, aromatic ring H), 6.99 (m, 1H, aromatic ring H), 6.21 (m, 1H, cyclopentadiene H), 6.10 (m, 1H, cyclopentadiene H), 4.66 (m, 2H, aromatic ring H), 2.90 (m, 2H, cyclopentadiene H), 0.85 (m, 10H, cyclohexyl H).

(embodiment 14) 3,6-difluoro substituted fluorene is part silicon bridge titanium catalyst even

(4) the 1 cyclohexyl chloride silane of 20mmol is dissolved in 50mL ether, is cooled to-78 DEG C, the butyl of dropping 20mmol Lithium, adds the titanium tetrachloride of 1eq after adding, go back after mixture is stirred overnight, and dropping 10mmol ligand is dissolved in 30ml ether In mixed liquor.After dropping, mixture is stirred overnight, and then evaporates solvent and with dichloromethane extracted residues, merges Organic facies, dried over sodium sulfate, filter and evaporate solvent the most under vacuo.For purification, residue is dissolved in pentane, molten Liquid filters through silica gel and i.e. can get corresponding 3-30 DEG C of crystallizations, and 6-difluoro fluorenes-2-fluorine cyclopentadiene-cyclohexyl chloride silane- Titanium chloride.Feature:¹H NMR(DMSO d⁶) δ ppm:7.55 (m, 4H, aromatic ring H), 7.28 (m, 1H, aromatic ring H), 6.99 (m, 2H, Aromatic ring H), 6.21 (m, 1H, cyclopentadiene H), 6.10 (m, 1H, cyclopentadiene H), 4.66 (m, 2H, aromatic ring H), 2.90 (m, 2H, Cyclopentadiene H), 0.85 (m, 10H, cyclohexyl H).

(embodiment 15) 3-ethyl substituted fluorene is part silicon bridge titanium catalyst even

(1) 3-ethyl substituted fluorene, with embodiment 3 step (1).

(4) the cyclohexyl chloride silane of 20mmol is dissolved in 50mL ether, is cooled to-78 DEG C, the butyl lithium of dropping 20mmol, Adding the titanium tetrachloride of 1eq after adding, go back after mixture is stirred overnight, dropping 10mmol ligand is dissolved in 30ml ether Mixed liquor.After dropping, mixture is stirred overnight, and then evaporates solvent and with dichloromethane extracted residues, merges organic Phase, dried over sodium sulfate, filter and evaporate solvent the most under vacuo.For purification, residue is dissolved in pentane, solution warp Silica gel filter and-30 DEG C crystallization i.e. can get corresponding 3-ethyl fluorenes-2-fluorine cyclopentadiene-cyclohexyl silica-based-titanium chloride. Feature:¹H NMR(DMSO d⁶) δ ppm:7.55 (m, 4H, aromatic ring H), 7.28 (m, 1H, aromatic ring H), 6.99 (m, 2H, aromatic ring H), 6.21 (m, 1H, cyclopentadiene H), 6.10 (m, 1H, cyclopentadiene H), 4.66 (m, 2H, aromatic ring H), 2.90 (m, 2H, cyclopentadiene H),2.60(m,2H,CH₂),1.25(m,3H,CH₃), 0.85 (m, 10H, cyclohexyl H).

(embodiment 16) 3-fluorine substituted fluorene is part silicon bridge hafnium metallic catalyst even

(1) synthesis of 3-fluorine substituted fluorene, with embodiment 1 step (1).

(4) the cyclohexyl chloride silane of 20mmol is dissolved in 50mL ether, is cooled to-78 DEG C, the butyl lithium of dropping 20mmol, Adding the hafnium tetrachloride of 1eq after adding, go back after mixture is stirred overnight, dropping 10mmol ligand is dissolved in 30ml ether Mixed liquor.After dropping, mixture is stirred overnight, and then evaporates solvent and with dichloromethane extracted residues, merges organic Phase, dried over sodium sulfate, filter and evaporate solvent the most under vacuo.For purification, residue is dissolved in pentane, solution warp Silica gel filter and-30 DEG C crystallization i.e. can get corresponding 3-fluorine fluorenes-2-fluorine cyclopentadiene-cyclohexyl silica-based-hafnium dichloride.Special Levy:¹H NMR(DMSO d⁶) δ ppm:7.87 (m, 1H, aromatic ring H) 7.55 (m, 3H, aromatic ring H), 7.38 (m, 1H, aromatic ring H), 7.28 (m, 1H, aromatic ring H), 6.99 (m, 1H, aromatic ring H), 6.21 (m, 1H, cyclopentadiene H), 6.10 (m, 1H, cyclopentadiene H), 4.66 (m, 2H, aromatic ring H), 2.90 (m, 2H, cyclopentadiene H), 0.85 (m, 10H, cyclohexyl H).

(embodiment 17) 3,6-difluoro substituted fluorene is part silicon bridge hafnium metallic catalyst even

(4) the cyclohexyl chloride silane of 20mmol is dissolved in 50mL ether, is cooled to-78 DEG C, the butyl lithium of dropping 20mmol, Adding the hafnium tetrachloride of 1eq after adding, go back after mixture is stirred overnight, dropping 10mmol ligand is dissolved in 30ml ether Mixed liquor.After dropping, mixture is stirred overnight, and then evaporates solvent and with dichloromethane extracted residues, merges organic Phase, dried over sodium sulfate, filter and evaporate solvent the most under vacuo.For purification, residue is dissolved in pentane, solution warp Silica gel filters and also i.e. can get corresponding 3-30 DEG C of crystallizations, and 6-difluoro fluorenes-2-fluorine cyclopentadiene-cyclohexyl is silica-based-dichloride Hafnium.Feature:¹H NMR(DMSO d⁶) δ ppm:7.55 (m, 4H, aromatic ring H), 7.28 (m, 1H, aromatic ring H), 6.99 (m, 2H, aromatic rings H), 6.21 (m, 1H, cyclopentadiene H), 6.10 (m, 1H, cyclopentadiene H), 4.66 (m, 2H, aromatic ring H), 2.90 (m, 2H, rings penta Diene H), 0.85 (m, 10H, cyclohexyl H).

(embodiment 18) 3-ethyl substituted fluorene is part silicon bridge hafnium metallic catalyst even

(1) 3-ethyl substituted fluorene, with embodiment 3 step (1).

(4) the cyclohexyl chloride silane of 20mmol is dissolved in 50mL ether, is cooled to-78 DEG C, the butyl of dropping 20mmol Lithium, adds the hafnium tetrachloride of 1eq after adding, go back after mixture is stirred overnight, and dropping 10mmol ligand is dissolved in 30ml ether In mixed liquor.After dropping, mixture is stirred overnight, and then evaporates solvent and with dichloromethane extracted residues, merges Organic facies, dried over sodium sulfate, filter and evaporate solvent the most under vacuo.For purification, residue is dissolved in pentane, molten Liquid through silica gel filter and-30 DEG C crystallization i.e. can get corresponding 3-ethyl fluorenes-2-fluorine cyclopentadiene-cyclohexyl silica-based-dichloro Change hafnium.Feature:¹H NMR(DMSO d⁶) δ ppm:7.55 (m, 4H, aromatic ring H), 7.28 (m, 1H, aromatic ring H), 6.99 (m, 2H, aromatic rings H), 6.40 (m, 4H, aromatic ring H), 6.21 (m, 1H, cyclopentadiene H), 6.10 (m, 1H, cyclopentadiene H), 4.66 (m, 2H, aromatic rings H), 2.90 (m, 2H, cyclopentadiene H), 2.60 (m, 2H, CH₂),1.25(m,3H,CH₃), 0.85 (m, 10H, cyclohexyl H).

(embodiment 19) 5H-indeno [1,2-b] pyridine radicals is the zirconium metal catalyzer of part carbon bridging

(1) synthesis of 2-fluorine cyclopentadienyl group: with example 1 step 2

(2) 10mmol 5H-indeno [1,2-b] pyridinium dissolution in 50ml ether and with the 1.6M of 10mmol n-BuLi Hexane solution mixes, and then stirs several hours.Add equimolar replacement 2-fluorine cyclopentadiene, and mixture is stirred overnight. Then with 50ml water hydrolysis reaction mixture, it is dried organic facies with sodium sulfate and evaporates solvent under vacuo, standby.

(3) the 1 of 20mmol, 3,5-trifluoro-benzenes are dissolved in 50mL ether, are cooled to-78 DEG C, the butyl lithium of dropping 20mmol, Adding the Zirconium tetrachloride. of 1eq after adding, go back after mixture is stirred overnight, dropping 10mmol ligand is dissolved in 30ml ether Mixed liquor.After dropping, mixture is stirred overnight, and then evaporates solvent and with dichloromethane extracted residues, merges organic Phase, dried over sodium sulfate, filter and evaporate solvent the most under vacuo.For purification, residue is dissolved in pentane, solution warp Silica gel filters and i.e. can get corresponding 5H-indeno [1,2-b] pyridine-2-fluorine cyclopentadiene-two-1,3,5--30 DEG C of crystallizations Trifluorophenyl-zirconium dichloride.Feature:¹H NMR(DMSO d⁶) δ ppm:8.50 (m, 1H, aromatic ring H), 7.95 (m, 1H, aromatic ring H), 7.85 (m, 1H, aromatic ring H), 7.60 (m, 1H, aromatic ring H), 7.40 (m, 1H, aromatic ring H), 7.15 (m, 1H, aromatic ring H), 6.40 (m, 4H, aromatic ring H), 6.21 (m, 1H, cyclopentadiene H), 6.10 (m, 1H, cyclopentadiene H), 2.90 (m, 2H, cyclopentadiene H), 2.65 (m, 2H, aromatic ring H).

(embodiment 20) 5H-indeno [1,2-b] pyridine radicals is the titanium catalyst of part carbon bridging

(1) synthesis of 2-fluorine cyclopentadienyl group, with embodiment 1 step (2).

(2) 10mmol 5H-indeno [1,2-b] pyridinium dissolution in 50ml ether and with the 1.6M of 10mmol n-BuLi Hexane solution mixes, and then stirs several hours.Add equimolar 2-fluorine cyclopentadienyl group (ibid) and mixture is stirred Night.Then with 50ml water hydrolysis reaction mixture, it is dried organic facies with sodium sulfate and evaporates solvent under vacuo, standby.

(3) the 1 of 20mmol, 3,5-trifluoro-benzenes are dissolved in 50mL ether, are cooled to-78 DEG C, the butyl lithium of dropping 20mmol, Adding the titanium tetrachloride of 1eq after adding, go back after mixture is stirred overnight, dropping 10mmol ligand is dissolved in 30ml ether Mixed liquor.After dropping, mixture is stirred overnight, and then evaporates solvent and with dichloromethane extracted residues, merges organic Phase, dried over sodium sulfate, filter and evaporate solvent the most under vacuo.For purification, residue is dissolved in pentane, solution warp Silica gel filters and i.e. can get corresponding 5H-indeno [1,2-b] pyridine-2-fluorine cyclopentadiene-two-1,3,5--30 DEG C of crystallizations Trifluorophenyl-titanium chloride.Feature:¹H NMR(DMSO d⁶) δ ppm:8.50 (m, 1H, aromatic ring H), 7.95 (m, 1H, aromatic ring H), 7.85 (m, 1H, aromatic ring H), 7.60 (m, 1H, aromatic ring H), 7.40 (m, 1H, aromatic ring H), 7.15 (m, 1H, aromatic ring H), 6.40 (m, 4H, aromatic ring H), 6.21 (m, 1H, cyclopentadiene H), 6.10 (m, 1H, cyclopentadiene H), 2.90 (m, 2H, cyclopentadiene H), 2.65 (m, 2H, aromatic ring H).

(embodiment 21) 5H-indeno [1,2-b] pyridine radicals is the hafnium metallic catalyst of part carbon bridging

(1) synthesis of 2-fluorine cyclopentadienyl group, with embodiment 1 step (2).

(3) the 1 of 20mmol, 3,5-trifluoro-benzenes are dissolved in 50mL ether, are cooled to-78 DEG C, the butyl lithium of dropping 20mmol, Adding the hafnium tetrachloride of 1eq after adding, go back after mixture is stirred overnight, dropping 10mmol ligand is dissolved in 30ml ether Mixed liquor.After dropping, mixture is stirred overnight, and then evaporates solvent and with dichloromethane extracted residues, is associated with Machine phase, dried over sodium sulfate, filter and evaporate solvent the most under vacuo.For purification, residue is dissolved in pentane, solution Filter through silica gel and i.e. can get corresponding 5H-indeno [1,2-b] pyridine-2-fluorine cyclopentadiene-two-1,3-30 DEG C of crystallizations, 5-trifluorophenyl-hafnium dichloride.Feature:¹H NMR(DMSO d⁶) 8.50 (m, 1H, aromatic ring H), 7.95 (m, 1H, aromatic ring H), 7.85 (m, 1H, aromatic ring H), 7.60 (m, 1H, aromatic ring H), 7.40 (m, 1H, aromatic ring H), 7.15 (m, 1H, aromatic ring H), 6.40 (m, 4H, virtues Ring H), 6.21 (m, 1H, cyclopentadiene H), 6.10 (m, 1H, cyclopentadiene H), 2.90 (m, 2H, cyclopentadiene H), 2.65 (m, 2H, aromatic ring H).

(embodiment 22) 5H-indeno [1,2-b] pyridine radicals is part silicon bridge zirconium metal catalyzer even

(1) synthesis of 2-fluorine cyclopentadienyl group: with embodiment 1 step (2).

(2) 5H-indeno [1,2-b] pyridinium dissolution in 50ml ether and with the 1.6M hexane solution of 10mmol n-BuLi Mixing, then stirs several hours.Add equimolar replacement 2-fluorine cyclopentadiene, and mixture is stirred overnight.Then with 50ml water hydrolysis reaction mixture, is dried organic facies with sodium sulfate and evaporates solvent under vacuo, standby.

(3) the cyclohexyl chloride silane of 20mmol is dissolved in 50mL ether, is cooled to-78 DEG C, the butyl lithium of dropping 20mmol, Adding the Zirconium tetrachloride. of 1eq after adding, go back after mixture is stirred overnight, dropping 10mmol ligand is dissolved in 30ml ether Mixed liquor.After dropping, mixture is stirred overnight, and then evaporates solvent and with dichloromethane extracted residues, merges organic Phase, dried over sodium sulfate, filter and evaporate solvent the most under vacuo.For purification, residue is dissolved in pentane, solution warp Silica gel filters and i.e. can get corresponding 5H-indeno [1,2-b] pyridine-2-fluorine cyclopentadiene-cyclohexyl silicon-30 DEG C of crystallizations Base-zirconium dichloride.Feature:¹H NMR(DMSO d⁶) δ ppm:8.50 (m, 1H, aromatic ring H), 7.95 (m, 1H, aromatic ring H), 7.85 (m, 1H, aromatic ring H), 7.60 (m, 1H, aromatic ring H), 7.40 (m, 1H, aromatic ring H), 7.15 (m, 1H, aromatic ring H), 6.21 (m, 1H, rings penta 2 Alkene H), 6.10 (m, 1H, cyclopentadiene H), 2.90 (m, 2H, cyclopentadiene H), 2.65 (m, 2H, aromatic ring H), 2.60 (m, 2H, CH₂),1.25(m,3H,CH₃), 0.85 (m, 10H, cyclohexyl H).(embodiment 23) 5H-indeno [1,2-b] pyridine radicals is part silicon The titanium catalyst of bridging

(1) synthesis of 2-fluorine cyclopentadienyl group: with embodiment 1 step (2).

(3) the cyclohexyl chloride silane of 20mmol is dissolved in 50mL ether, is cooled to-78 DEG C, the butyl lithium of dropping 20mmol, Adding the titanium tetrachloride of 1eq after adding, go back after mixture is stirred overnight, dropping 10mmol ligand is dissolved in 30ml ether Mixed liquor.After dropping, mixture is stirred overnight, and then evaporates solvent and with dichloromethane extracted residues, merges organic Phase, dried over sodium sulfate, filter and evaporate solvent the most under vacuo.For purification, residue is dissolved in pentane, solution warp Silica gel filters and i.e. can get corresponding 5H-indeno [1,2-b] pyridine-2-fluorine cyclopentadiene-cyclohexyl silicon-30 DEG C of crystallizations Base-titanium chloride.Feature:¹H NMR(DMSO d⁶) δ ppm:8.50 (m, 1H, aromatic ring H), 7.95 (m, 1H, aromatic ring H), 7.85 (m, 1H, aromatic ring H), 7.60 (m, 1H, aromatic ring H), 7.40 (m, 1H, aromatic ring H), 7.15 (m, 1H, aromatic ring H), 6.21 (m, 1H, rings penta 2 Alkene H), 6.10 (m, 1H, cyclopentadiene H), 2.90 (m, 2H, cyclopentadiene H), 2.65 (m, 2H, aromatic ring H), 2.60 (m, 2H, CH₂),1.25(m,3H,CH₃), 0.85 (m, 10H, cyclohexyl H).(embodiment 24) 5H-indeno [1,2-b] pyridine radicals is part silicon The hafnium metallic catalyst of bridging

(1) synthesis of 2-fluorine cyclopentadienyl group: with embodiment 1 step (2).

(3) the cyclohexyl chloride silane of 20mmol is dissolved in 50mL ether, is cooled to-78 DEG C, the butyl lithium of dropping 20mmol, Adding the hafnium tetrachloride of 1eq after adding, go back after mixture is stirred overnight, dropping 10mmol ligand is dissolved in 30ml ether Mixed liquor.After dropping, mixture is stirred overnight, and then evaporates solvent and with dichloromethane extracted residues, merges organic Phase, dried over sodium sulfate, filter and evaporate solvent the most under vacuo.For purification, residue is dissolved in pentane, solution warp Silica gel filters and i.e. can get corresponding 5H-indeno [1,2-b] pyridine-2-fluorine cyclopentadiene-cyclohexyl silicon-30 DEG C of crystallizations Base-hafnium dichloride.Feature:¹H NMR(DMSO d⁶) δ ppm:8.50 (m, 1H, aromatic ring H), 7.95 (m, 1H, aromatic ring H), 7.85 (m, 1H, aromatic ring H), 7.60 (m, 1H, aromatic ring H), 7.40 (m, 1H, aromatic ring H), 7.15 (m, 1H, aromatic ring H), 6.21 (m, 1H, rings penta 2 Alkene H), 6.10 (m, 1H, cyclopentadiene H), 2.90 (m, 2H, cyclopentadiene H), 2.65 (m, 2H, aromatic ring H), 2.60 (m, 2H, CH₂),1.25(m,3H,CH₃), 0.85 (m, 10H, cyclohexyl H).

(embodiment 25) 5H-indeno [1,2-b] thiopyranyl is the zirconium metal catalyzer of part carbon bridging

(1) synthesis of 2-fluorine cyclopentadienyl group: with example 1 step 2

(2) 10mmol 5H-indeno [1,2-b] thio-pyrylium be dissolved in 50ml ether and with 10mmol n-BuLi 1.6M hexane solution mixes, and then stirs several hours.Add equimolar replacement 2-fluorine cyclopentadiene, and mixture is stirred Night.Then with 50ml water hydrolysis reaction mixture, it is dried organic facies with sodium sulfate and evaporates solvent under vacuo, standby.

(3) the 1 of 20mmol, 3,5-trifluoro-benzenes are dissolved in 50mL ether, are cooled to-78 DEG C, the butyl lithium of dropping 20mmol, Adding the Zirconium tetrachloride. of 1eq after adding, go back after mixture is stirred overnight, dropping 10mmol ligand is dissolved in 30ml ether Mixed liquor.After dropping, mixture is stirred overnight, and then evaporates solvent and with dichloromethane extracted residues, merges organic Phase, dried over sodium sulfate, filter and evaporate solvent the most under vacuo.For purification, residue is dissolved in pentane, solution warp Silica gel filters and i.e. can get corresponding 5H-indeno [1,2-b] thio-pyrylium-2-fluorine cyclopentadiene-two-1-30 DEG C of crystallizations, 3,5-trifluorophenyls-zirconium dichloride.Feature:¹H NMR(DMSO d⁶) δ ppm:8.90 (m, 1H, aromatic ring H), 8.35 (m, 1H, aromatic rings H), 8.25 (m, 1H, aromatic ring H), 8.00 (m, 1H, aromatic ring H), 7.80 (m, 1H, aromatic ring H), 7.55 (m, 1H, aromatic ring H), 6.40 (m, 4H, aromatic ring H), 6.21 (m, 1H, cyclopentadiene H), 6.10 (m, 1H, cyclopentadiene H), 2.90 (m, 2H, cyclopentadiene H), 2.65 (m, 2H, aromatic ring H).

(embodiment 26) 5H-indeno [1,2-b] thiopyranyl is the titanium catalyst of part carbon bridging

(1) synthesis of 2-fluorine cyclopentadienyl group, with embodiment 1 step (2).

(2) 10mmol 5H-indeno [1,2-b] thio-pyrylium be dissolved in 50ml ether and with 10mmol n-BuLi 1.6M hexane solution mixes, and then stirs several hours.Add equimolar 2-fluorine cyclopentadienyl group (ibid) and mixture stirs Mix overnight.Then with 50ml water hydrolysis reaction mixture, it is dried organic facies with sodium sulfate and evaporates solvent under vacuo, standby.

(3) the 1 of 20mmol, 3,5-trifluoro-benzenes are dissolved in 50mL ether, are cooled to-78 DEG C, the butyl lithium of dropping 20mmol, Adding the titanium tetrachloride of 1eq after adding, go back after mixture is stirred overnight, dropping 10mmol ligand is dissolved in 30ml ether Mixed liquor.After dropping, mixture is stirred overnight, and then evaporates solvent and with dichloromethane extracted residues, merges organic Phase, dried over sodium sulfate, filter and evaporate solvent the most under vacuo.For purification, residue is dissolved in pentane, solution warp Silica gel filters and i.e. can get corresponding 5H-indeno [1,2-b] thio-pyrylium-2-fluorine cyclopentadiene-two-1-30 DEG C of crystallizations, 3,5-trifluorophenyls-titanium chloride.Feature:¹H NMR(DMSO d⁶) δ ppm:8.90 (m, 1H, aromatic ring H), 8.35 (m, 1H, aromatic rings H), 8.25 (m, 1H, aromatic ring H), 8.00 (m, 1H, aromatic ring H), 7.80 (m, 1H, aromatic ring H), 7.55 (m, 1H, aromatic ring H), 6.40 (m, 4H, aromatic ring H), 6.21 (m, 1H, cyclopentadiene H), 6.10 (m, 1H, cyclopentadiene H), 2.90 (m, 2H, cyclopentadiene H), 2.65 (m, 2H, aromatic ring H).

(embodiment 27) 5H-indeno [1,2-b] thiopyranyl is the hafnium metallic catalyst of part carbon bridging

(1) synthesis of 2-fluorine cyclopentadienyl group, with embodiment 1 step (2).

(3) the 1 of 20mmol, 3,5-trifluoro-benzenes are dissolved in 50mL ether, are cooled to-78 DEG C, the butyl lithium of dropping 20mmol, Adding the hafnium tetrachloride of 1eq after adding, go back after mixture is stirred overnight, dropping 10mmol ligand is dissolved in 30ml ether Mixed liquor.After dropping, mixture is stirred overnight, and then evaporates solvent and with dichloromethane extracted residues, merges organic Phase, dried over sodium sulfate, filter and evaporate solvent the most under vacuo.For purification, residue is dissolved in pentane, solution warp Silica gel filter and-30 DEG C of crystallizations i.e. can get corresponding 5H-indeno [1,2-b] thio-pyrylium pyridine-2-fluorine cyclopentadiene-two- 1,3,5-trifluorophenyl-hafnium dichloride.Feature:¹H NMR(DMSO d⁶) 8.90 (m, 1H, aromatic ring H), 8.35 (m, 1H, aromatic ring H), 8.25 (m, 1H, aromatic ring H), 8.00 (m, 1H, aromatic ring H), 7.80 (m, 1H, aromatic ring H), 7.55 (m, 1H, aromatic ring H), 6.40 (m, 4H, aromatic ring H), 6.21 (m, 1H, cyclopentadiene H), 6.10 (m, 1H, cyclopentadiene H), 2.90 (m, 2H, cyclopentadiene H), 2.65 (m, 2H, aromatic ring H).

(embodiment 28) 5H-indeno [1,2-b] thiopyranyl is part silicon bridge zirconium metal catalyzer even

(1) synthesis of 2-fluorine cyclopentadienyl group: with embodiment 1 step (2).

(2) 5H-indeno [1,2-b] thio-pyrylium be dissolved in 50ml ether and with the 1.6M hexane of 10mmol n-BuLi Solution mixes, and then stirs several hours.Add equimolar replacement 2-fluorine cyclopentadiene, and mixture is stirred overnight.Then With 50ml water hydrolysis reaction mixture, it is dried organic facies with sodium sulfate and evaporates solvent under vacuo, standby.

(3) the cyclohexyl chloride silane of 20mmol is dissolved in 50mL ether, is cooled to-78 DEG C, the butyl lithium of dropping 20mmol, Adding the Zirconium tetrachloride. of 1eq after adding, go back after mixture is stirred overnight, dropping 10mmol ligand is dissolved in 30ml ether Mixed liquor.After dropping, mixture is stirred overnight, and then evaporates solvent and with dichloromethane extracted residues, merges organic Phase, dried over sodium sulfate, filter and evaporate solvent the most under vacuo.For purification, residue is dissolved in pentane, solution warp Silica gel filters and i.e. can get corresponding 5H-indeno [1,2-b] thio-pyrylium-2-fluorine cyclopentadiene-cyclohexyl-30 DEG C of crystallizations Silica-based-zirconium dichloride.Feature:¹H NMR(DMSO d⁶) δ ppm:8.90 (m, 1H, aromatic ring H), 8.35 (m, 1H, aromatic ring H), 8.25 (m, 1H, aromatic ring H), 8.00 (m, 1H, aromatic ring H), 7.80 (m, 1H, aromatic ring H), 7.55 (m, 1H, aromatic ring H), 6.21 (m, 1H, rings Pentadiene H), 6.10 (m, 1H, cyclopentadiene H), 2.90 (m, 2H, cyclopentadiene H), 2.65 (m, 2H, aromatic ring H), 2.60 (m, 2H,CH₂),1.25(m,3H,CH₃), 0.85 (m, 10H, cyclohexyl H).

(embodiment 29) 5H-indeno [1,2-b] thiopyranyl is part silicon bridge titanium catalyst even

(1) synthesis of 2-fluorine cyclopentadienyl group: with embodiment 1 step (2).

(3) the cyclohexyl chloride silane of 20mmol is dissolved in 50mL ether, is cooled to-78 DEG C, the butyl lithium of dropping 20mmol, Adding the titanium tetrachloride of 1eq after adding, go back after mixture is stirred overnight, dropping 10mmol ligand is dissolved in 30ml ether Mixed liquor.After dropping, mixture is stirred overnight, and then evaporates solvent and with dichloromethane extracted residues, merges organic Phase, dried over sodium sulfate, filter and evaporate solvent the most under vacuo.For purification, residue is dissolved in pentane, solution warp Silica gel filters and i.e. can get corresponding 5H-indeno [1,2-b] thio-pyrylium-2-fluorine cyclopentadiene-cyclohexyl-30 DEG C of crystallizations Silica-based-titanium chloride.Feature:¹H NMR(DMSO d⁶) δ ppm:8.50 (m, 1H, aromatic ring H), 7.95 (m, 1H, aromatic ring H), 7.85 (m, 1H, aromatic ring H), 7.60 (m, 1H, aromatic ring H), 7.40 (m, 1H, aromatic ring H), 7.15 (m, 1H, aromatic ring H), 6.21 (m, 1H, rings Pentadiene H), 6.10 (m, 1H, cyclopentadiene H), 2.90 (m, 2H, cyclopentadiene H), 2.65 (m, 2H, aromatic ring H), 2.60 (m, 2H,CH₂),1.25(m,3H,CH₃), 0.85 (m, 10H, cyclohexyl H).

(embodiment 30) 5H-indeno [1,2-b] thiopyranyl is part silicon bridge hafnium metallic catalyst even

(1) synthesis of 2-fluorine cyclopentadienyl group: with embodiment 1 step (2).

(3) the cyclohexyl chloride silane of 20mmol is dissolved in 50mL ether, is cooled to-78 DEG C, the butyl lithium of dropping 20mmol, Adding the hafnium tetrachloride of 1eq after adding, go back after mixture is stirred overnight, dropping 10mmol ligand is dissolved in 30ml ether Mixed liquor.After dropping, mixture is stirred overnight, and then evaporates solvent and with dichloromethane extracted residues, is associated with Machine phase, dried over sodium sulfate, filter and evaporate solvent the most under vacuo.For purification, residue is dissolved in pentane, solution Filter through silica gel and i.e. can get corresponding 5H-indeno [1,2-b] thio-pyrylium-2-fluorine cyclopentadiene-hexamethylene-30 DEG C of crystallizations Base is silica-based-hafnium dichloride.Feature:¹H NMR(DMSO d⁶) δ ppm:8.50 (m, 1H, aromatic ring H), 7.95 (m, 1H, aromatic ring H), 7.85 (m, 1H, aromatic ring H), 7.60 (m, 1H, aromatic ring H), 7.40 (m, 1H, aromatic ring H), 7.15 (m, 1H, aromatic ring H), 6.21 (m, 1H, cyclopentadiene H), 6.10 (m, 1H, cyclopentadiene H), 2.90 (m, 2H, cyclopentadiene H), 2.65 (m, 2H, aromatic ring H), 2.60 (m,2H,CH₂),1.25(m,3H,CH₃), 0.85 (m, 10H, cyclohexyl H).

Particular embodiments described above, has been carried out the purpose of the present invention, technical scheme and beneficial effect the most in detail Describe in detail bright, be it should be understood that the specific embodiment that the foregoing is only the present invention, be not limited to the present invention, all Within the spirit and principles in the present invention, any modification, equivalent substitution and improvement etc. done, should be included in the guarantor of the present invention Within the scope of protecting.

Catalyst activity test experiments:

Primary raw material and pretreatment thereof:

The operation being related to metal-organic preparation and process all uses standard glove box and Schlenk skill Art, is carried out under high pure nitrogen.Solvent toluene, analytical pure, use more than front metallic sodium and benzophenone continuous backflow 24h straight To variable color, distillation seals standby.1-decene for polyreaction purchased from Aldrich and carries out pure by water and oxygen scavenger Change.The evacuated deoxygenation of polymerization experiment reaction bulb dehumidifies, and replaces at least 3～4 times with high pure nitrogen, nitrogen protection borehole cooling. Prepare the toluene solution of certain density major catalyst and promoter.When oil bath temperature reaches design temperature, use and be dried Glass syringe add in glass reaction bottle and be sequentially added into 1-decene, toluene under a certain amount of promoter, stirring, advocate peace The toluene solution of cocatalyst, keeps oil bath temperature, starts polymerization.After reaction certain time, terminate with alcohol hydrochloric acid solution Reaction, then carries out polymerizate filtering separating.By upper strata product add deionized water rinsing several times after, carry out at separatory Reason, takes the supernatant and unreacted monomer and solvent is distilled off through normal pressure, then obtain 90～160 DEG C of interval decompression distillations Target product.The concentration of catalytic component is as follows: metallocene catalyst: the toluene solution of 1%；Main promoter: 0.1%Ph₃C⁺ B(C₆F₅)₄ ^-Toluene solution；Cocatalyst: 25%Al (iBu)₃Toluene solution.

Three kinds of catalytic components: the mol ratio of metallocene catalyst/main promoter/cocatalyst is 1:2:6.

Experimental technique:

Dry 50ml toluene and 1-decene (370g, 2.64mol) are joined 1 500ml with magnetic agitation In reaction bulb.In time being warming up to 50 DEG C, it is separately added into 20ml auxiliary catalysis agent solution (0.30g, 1.00mmol) and stirs 30 points Clock.Then by the catalyst mixture 5ml of activation, including metallocene catalyst (X, 0.010mmol Zr), main promoter [CPh₃]⁺[B(C₆F₅)₄]^-(0.18g, 0.020mmol) and cocatalyst (iBu)₃The toluene of Al (0.10g, 0.50mmol) is molten Liquid is injected in reaction bulb and makes it start reaction, and heating makes reaction temperature rise to 70 DEG C, maintains isothermal reaction 1 hour.Then Add 5ml alcohol hydrochloric acid solution and terminate reaction.After removing unreacted 1-decene and solvent toluene under vacuum, weigh residue and produce The weight of thing, calculates catalysis activity and 1-decene conversion ratio.

Example 1: metallocene catalyst: 3-fluorine fluorenes-2-fluorine cyclopentadiene-two-1,3,5-trifluorophenyls-zirconium dichloride

Example 2: metallocene catalyst: 3,6-difluoro fluorenes-2-fluorine cyclopentadiene-two-1,3,5-trifluorophenyls-zirconium dichloride

Example 3: metallocene catalyst: 3-ethyl fluorenes-2-fluorine cyclopentadiene-two-1,3,5-trifluorophenyls-zirconium dichloride

Example 4: metallocene catalyst: 3-fluorine fluorenes-2-fluorine cyclopentadiene-two-1,3,5-trifluorophenyls-titanium chloride

Example 5: metallocene catalyst: 3,6-difluoro fluorenes-2-fluorine cyclopentadiene-two-1,3,5-trifluorophenyls-titanium chloride

Example 6: metallocene catalyst: 3-ethyl fluorenes-2-fluorine cyclopentadiene-two-1,3,5-trifluorophenyls-titanium chloride

Example 7: metallocene catalyst: 3-fluorine fluorenes-2-fluorine cyclopentadiene-two-1,3,5-trifluorophenyls-hafnium dichloride

Example 8: metallocene catalyst: 3,6-difluoro fluorenes-2-fluorine cyclopentadiene-two-1,3,5-trifluorophenyls-hafnium dichloride

Example 9: metallocene catalyst: 3-ethyl fluorenes-2-fluorine cyclopentadiene-two-1,3,5-trifluorophenyls-hafnium dichloride

Example 10: metallocene catalyst: 3-fluorine fluorenes-2-fluorine cyclopentadiene-cyclohexyl methyl silicon-zirconium dichloride

Experimental result conclusive table 1

To sum up, metallocene poly-alpha olefins catalyst of the present invention, Stability Analysis of Structures, catalytic efficiency is high, the preparation method of the present invention Easy and simple to handle, productivity is high, raw material is easy to get, low cost, environmental pollution are little, it is easy to industrialized production.

Claims

1. a synthetic lubricant base oil metallocene poly-alpha olefins catalyst, it is characterised in that: its structure is by substituted aroma Base, bridging silicon or carbon atom, 3 monosubstituted or 3,6 dibasic fluorenyls or 3 monosubstituted or 3,6-bis-is substituted 5H-indeno [1,2-b] pyridine radicals or 3 monosubstituted or 3,6-bis-substituted 5H-indeno [1,2-b] thiopyranyl, metal Dentate five part forms, and its structural formula is:

X=C, S, N

Y=Si, C

M=Zr, Hf, Ti

R₂It is substituent group on benzothiophene, for fluorine atom or hydrogen atom；R₃It is substituent group on indole, former for fluorine atom or hydrogen Son；R₄It is the substituent group on the silicon atom of bridging, for cyclohexyl, cyclopenta, cyclobutyl；When bridge formation atom is carbon, substituent group It is 1,3,5-tri-replacements or monosubstituted dibasic phenyl；

R₅It is 3 monosubstituted or bis-substituted fluorenyls of 3,6-or 3 monosubstituted or 3,6-bis-substituted 5H-indeno [1,2-b] pyridines Base or 3 monosubstituted or 3,6-bis-substituted 5H-indeno [1,2-b] thiopyranyl, R₅Be carbon number 2～24 all directly One of chain, the alkane of side chain, halogen；

M is metal zirconium or hafnium or titanium；

L is the halogen with metal-complexing.

Synthetic lubricant base oil metallocene poly-alpha olefins catalyst the most according to claim 1, it is characterised in that: institute State R₅It is:

1) fluorenyl: 3-fluorine fluorenyl, 3,6-difluoro fluorenyl, 3-bromine fluorenyl, 3,6-dibromo fluorenyl, 3-iodine fluorenyl, 3,6-diiodo-fluorenyl, 3-ethylfluorenyl, 3,6-diethyl fluorenyl, 3-propyl group fluorenyl, 3,6-dipropyl fluorenyl, 3-butyl base fluorenyl, 3,6-dibutyl fluorenes Base, 3-isopropyl fluorenyl, 3,6-diisopropyl fluorenyl, 3-isobutyl group base fluorenyl, 3,6-diisobutyl fluorenyl, 3-amyl group fluorenyl, 3,6-diamyl fluorenyls, 3-isopentyl fluorenyl, 3,6-diisoamyl fluorenyl, 3-tert-butyl group base fluorenyl, 3,6-di-t-butyl base fluorenes Base, 3-pi-allyl fluorenyl, 3,6-diallyl base fluorenyl, 3-hexyl fluorenyl, 3,6-dihexyl fluorenyl, 3-isohesyl fluorenyl, 3, 6-bis-isohesyl fluorenyl, 3-t-butylethyl fluorenyl, 3,6-di-t-butyl ethylfluorenyl, 3-heptyl fluorenyl, 3,6-diheptyl fluorenes Base, 3-different heptyl fluorenyl, 3,6-bis-different heptyl fluorenyl, 3-tert-butyl group propyl group fluorenyl, 3,6-di-t-butyl propyl group fluorenyl, 3-octyl group Fluorenyl, 3,6-dioctyl fluorenyl, 3-iso-octyl fluorenyl, 3,6-diisooctyl fluorenyl, 3-tert-butyl group butyl fluorenyl, 3,6-bis-uncle Butyl fluorenyl, 3-undecyl fluorenyl, 3,6-bis--undecyl fluorenyl, 3-dodecyl fluorenyl, 3,6-bis--dodecane Base fluorenyl, 3-tridecyl fluorenyl, 3,6-bis--tridecyl fluorenyl, 3-myristyl fluorenyl, 3,6-bis--myristyl fluorenyl, 3-pentadecyl fluorenyl, 3,6-bis--pentadecyl fluorenyl, 3-cetyl fluorenyl, 3,6-bis--cetyl fluorenyl, 3-17 Alkyl fluorenyl, 3,6-bis--heptadecyl fluorenyl, 3-octadecyl fluorenyl, 3,6-bis--octadecyl fluorenyl, 3-nonadecyl fluorenes Base, 3,6-bis--nonadecyl fluorenyl, 3-eicosyl fluorenyl, 3,6-bis--eicosyl fluorenyl, 3-heneicosyl fluorenyl, 3, 6-bis--heneicosyl fluorenyl, 3-docosyl fluorenyl, 3,6-bis--docosyl fluorenyl, 3-tricosyl fluorenyl, 3,6-bis--tricosyl fluorenyls, 3-tetracosyl fluorenyl, 3, one of 6-bis--tetracosyl fluorenyl；

2) 5H-indeno [1,2-b] pyridine radicals: 3-fluorine 5H-indeno [1,2-b] pyridine radicals, 3,6-difluoro 5H-indeno [1,2-b] pyrrole Piperidinyl, 3-bromine 5H-indeno [1,2-b] pyridine radicals, 3,6-dibromo 5H-indeno [1,2-b] pyridine radicals, 3-iodine 5H-indeno [1,2-b] Pyridine radicals, 3,6-diiodo-5H-indeno [1,2-b] pyridine radicals, 3-ethyl 5H-indeno [1,2-b] pyridine radicals, 3,6-diethyl 5H- Indeno [1,2-b] pyridine radicals, 3-propyl group 5H-indeno [1,2-b] pyridine radicals, 3,6-dipropyl 5H-indeno [1,2-b] pyridine radicals, 3-butyl 5H-indeno [1,2-b] pyridine radicals, 3,6-dibutyl 5H-indeno [1,2-b] pyridine radicals, 3-isopropyl 5H-indeno [1, 2-b] pyridine radicals, 3,6-diisopropyl 5H-indeno [1,2-b] pyridine radicals, 3-isobutyl group base 5H-indeno [1,2-b] pyridine radicals, 3, 6-diisobutyl 5H-indeno [1,2-b] pyridine radicals, 3-amyl group 5H-indeno [1,2-b] pyridine radicals, 3,6-diamyl 5H-indeno [1,2-b] pyridine radicals, 3-isopentyl 5H-indeno [1,2-b] pyridine radicals, 3,6-diisoamyl 5H-indeno [1,2-b] pyridine radicals, 3-tert-butyl group 5H-indeno [1,2-b] pyridine radicals, 3,6-di-t-butyl 5H-indeno [1,2-b] pyridine radicals, 3-pi-allyl 5H-indeno [1,2-b] pyridine radicals, 3,6-diallyl 5H-indeno [1,2-b] pyridine radicals, 3-hexyl 5H-indeno [1,2-b] pyridine radicals, 3, 6-dihexyl 5H-indeno [1,2-b] pyridine radicals, 3-isohesyl 5H-indeno [1,2-b] pyridine radicals, 3,6-bis-isohesyl 5H-indeno [1,2-b] pyridine radicals, 3-t-butylethyl 5H-indeno [1,2-b] pyridine radicals, 3,6-di-t-butyl ethyl 5H-indeno [1,2-b] Pyridine radicals, 3-heptyl 5H-indeno [1,2-b] pyridine radicals, 3,6-diheptyl 5H-indeno [1,2-b] pyridine radicals, 3-different heptyl 5H- Indeno [1,2-b] pyridine radicals, 3,6-bis-different heptyl 5H-indeno [1,2-b] pyridine radicals, 3-tert-butyl group propyl group 5H-indeno [1,2-b] Pyridine radicals, 3,6-di-t-butyl propyl group 5H-indeno [1,2-b] pyridine radicals, 3-octyl group 5H-indeno [1,2-b] pyridine radicals, 3,6-bis- Octyl group 5H-indeno [1,2-b] pyridine radicals, 3-iso-octyl 5H-indeno [1,2-b] pyridine radicals, 3,6-diisooctyl 5H-indeno [1, 2-b] pyridine radicals, 3-tert-butyl group butyl 5H-indeno [1,2-b] pyridine radicals, 3,6-di-t-butyl butyl 5H-indeno [1,2-b] pyrrole Piperidinyl, 3-undecyl 5H-indeno [1,2-b] pyridine radicals, 3,6-bis--undecyl 5H-indeno [1,2-b] pyridine radicals, 3-ten Dialkyl group 5H-indeno [1,2-b] pyridine radicals, 3,6-bis--dodecyl 5H-indeno [1,2-b] pyridine radicals, 3-tridecyl 5H- Indeno [1,2-b] pyridine radicals, 3,6-bis--tridecyl 5H-indeno [1,2-b] pyridine radicals, 3-myristyl 5H-indeno [1,2- B] pyridine radicals, 3,6-bis--myristyl 5H-indeno [1,2-b] pyridine radicals, 3-pentadecyl 5H-indeno [1,2-b] pyridine radicals, 3,6-bis--pentadecyl 5H-indeno [1,2-b] pyridine radicals, 3-cetyl 5H-indeno [1,2-b] pyridine radicals, 3,6-bis--ten Six alkyl 5H-indeno [1,2-b] pyridine radicals, 3-heptadecyl 5H-indeno [1,2-b] pyridine radicals, 3,6-bis--heptadecyl 5H- Indeno [1,2-b] pyridine radicals, 3-octadecyl 5H-indeno [1,2-b] pyridine radicals, 3,6-bis--octadecyl 5H-indeno [1,2- B] pyridine radicals, 3-nonadecyl 5H-indeno [1,2-b] pyridine radicals, 3,6-bis--nonadecyl 5H-indeno [1,2-b] pyridine radicals, 3-eicosyl 5H-indeno [1,2-b] pyridine radicals, 3,6-bis--eicosyl 5H-indeno [1,2-b] pyridine radicals, 3-heneicosane Base 5H-indeno [1,2-b] pyridine radicals, 3,6-bis--heneicosyl 5H-indeno [1,2-b] pyridine radicals, 3-docosyl 5H- Indeno [1,2-b] pyridine radicals, 3,6-bis--docosyl 5H-indeno [1,2-b] pyridine radicals, 3-tricosyl 5H-indeno [1,2-b] pyridine radicals, 3,6-bis--tricosyl 5H-indeno [1,2-b] pyridine radicals, 3-tetracosyl 5H-indeno [1,2- B] pyridine radicals, 3, one of 6-bis--tetracosyl 5H-indeno [1,2-b] pyridine radicals；

3) 5H-indeno [1,2-b] thiopyranyl: 3-fluorine 5H-indeno [1,2-b] thiopyranyl, 3,6-difluoro 5H-indeno [1,2-b] thiopyranyl, 3-bromine 5H-indeno [1,2-b] thiopyranyl, 3,6-dibromo 5H-indeno [1,2-b] thio-pyrylium Base, 3-iodine 5H-indeno [1,2-b] thiopyranyl, 3,6-diiodo-5H-indeno [1,2-b] thiopyranyl, 3-ethyl 5H-indenes And [1,2-b] thiopyranyl, 3,6-diethyl 5H-indeno [1,2-b] thiopyranyl, 3-propyl group 5H-indeno [1,2-b] sulfur For pyranose, 3,6-dipropyl 5H-indeno [1,2-b] thiopyranyl, 3-butyl 5H-indeno [1,2-b] thiopyranyl, 3, 6-dibutyl 5H-indeno [1,2-b] thiopyranyl, 3-isopropyl 5H-indeno [1,2-b] thiopyranyl, 3,6-diisopropyl Base 5H-indeno [1,2-b] thiopyranyl, 3-isobutyl group 5H-indeno [1,2-b] thiopyranyl, 3,6-diisobutyl 5H- Indeno [1,2-b] thiopyranyl, 3-amyl group 5H-indeno [1,2-b] thiopyranyl, 3,6-diamyl 5H-indeno [1,2-b] Thiopyranyl, 3-isopentyl 5H-indeno [1,2-b] thiopyranyl, 3,6-diisoamyl 5H-indeno [1,2-b] sulfur is for pyrrole Mutter base, 3-tert-butyl group base 5H-indeno [1,2-b] thiopyranyl, 3,6-di-t-butyl 5H-indeno [1,2-b] thiopyranyl, 3-pi-allyl 5H-indeno [1,2-b] thiopyranyl, 3,6-diallyl 5H-indeno [1,2-b] thiopyranyl, 3-hexyl 5H-indeno [1,2-b] thiopyranyl, 3,6-dihexyl 5H-indeno [1,2-b] thiopyranyl, 3-isohesyl 5H-indeno [1,2-b] thiopyranyl, 3,6-bis-isohesyl 5H-indeno [1,2-b] thiopyranyl, 3-t-butylethyl 5H-indeno [1, 2-b] thiopyranyl, 3,6-di-t-butyl ethyl 5H-indeno [1,2-b] thiopyranyl, 3-heptyl 5H-indeno [1,2-b] Thiopyranyl, 3,6-diheptyl 5H-indeno [1,2-b] thiopyranyl, 3-different heptyl 5H-indeno [1,2-b] thio-pyrylium Base, 3,6-bis-different heptyl 5H-indeno [1,2-b] thiopyranyl, 3-tert-butyl group propyl group 5H-indeno [1,2-b] thiopyranyl, 3,6-di-t-butyl propyl group 5H-indeno [1,2-b] thiopyranyl, 3-octyl group 5H-indeno [1,2-b] thiopyranyl, 3,6- Dioctyl 5H-indeno [1,2-b] thiopyranyl, 3-iso-octyl 5H-indeno [1,2-b] thiopyranyl, 3,6-diisooctyl 5H-indeno [1,2-b] thiopyranyl, 3-tert-butyl group butyl 5H-indeno [1,2-b] thiopyranyl, 3,6-di-t-butyl fourth Base 5H-indeno [1,2-b] thiopyranyl, 3-undecyl 5H-indeno [1,2-b] thiopyranyl, 3,6-bis--undecyl 5H-indeno [1,2-b] thiopyranyl, 3-dodecyl 5H-indeno [1,2-b] thiopyranyl, 3,6-bis--dodecyl 5H-indeno [1,2-b] thiopyranyl, 3-tridecyl 5H-indeno [1,2-b] thiopyranyl, 3,6-bis--tridecyl 5H-indeno [1,2-b] thiopyranyl, 3-myristyl 5H-indeno [1,2-b] thiopyranyl, 3,6-bis--myristyl 5H-indeno [1,2-b] thiopyranyl, 3-pentadecyl 5H-indeno [1,2-b] thiopyranyl, 3,6-bis--pentadecyl 5H-indeno [1,2-b] thiopyranyl, 3-cetyl 5H-indeno [1,2-b] thiopyranyl, 3,6-bis--cetyl 5H-indeno [1,2-b] thiopyranyl, 3-heptadecyl 5H-indeno [1,2-b] thiopyranyl, 3,6-bis--heptadecyl 5H-indeno [1,2-b] thiopyranyl, 3-octadecyl 5H-indeno [1,2-b] thiopyranyl, 3,6-bis--octadecyl 5H-indeno [1,2-b] thiopyranyl, 3-nonadecyl 5H-indeno [1,2-b] thiopyranyl, 3,6-bis--nonadecyl 5H-indeno [1,2-b] thiopyranyl, 3-eicosyl 5H-indeno [1,2-b] thiopyranyl, 3,6-bis--eicosyl 5H-indeno [1,2-b] thiopyranyl, 3-heneicosyl 5H-indeno [1,2-b] thiopyranyl, 3,6-bis--heneicosane Base 5H-indeno [1,2-b] thiopyranyl, 3-docosyl 5H-indeno [1,2-b] thiopyranyl, 3,6-bis--two 12 Alkyl 5H-indeno [1,2-b] thiopyranyl, 3-tricosyl 5H-indeno [1,2-b] thiopyranyl, 3,6-bis--two ten Trialkyl 5H-indeno [1,2-b] thiopyranyl, 3-tetracosyl 5H-indeno [1,2-b] thiopyranyl, 3,6-bis--two One of myristyl 5H-indeno [1,2-b] thiopyranyl.

3. the preparation side of a synthetic lubricant base oil metallocene poly-alpha olefins catalyst as claimed in claim 1 or 2 Method, it is characterised in that: the method comprising the steps of (1) prepare 3 monosubstituted or 3,6-bis-substituted fluorene radical derivative；(2) preparation replaces Cyclopentadienyl group, benzothienyl, indyl, 2,3,4,5-tetra-fluoro-1-methylindenyl；(3) preparation replacement fluorenyl takes in (2) For polymerization of olefin using catalyst body lithium salts；(4) bridging substituent group and coordination metal compound are prepared, then by the second of the ligand lithium salts in (3) Ethereal solution reacts with the coordination metal compound in (4), to obtain corresponding metallocene poly-alpha olefins catalyst.

The preparation method of synthetic lubricant base oil metallocene poly-alpha olefins catalyst the most according to claim 1 and 2, It is characterized in that: described step (3) substrate when being fluorenyl is: a: fluorenyl and cyclopentadienyl group: by 3 monosubstituted or 3,6-bis-replacements Fluorenyl derivative is dissolved in ether and mixes with the hexane solution of n-BuLi, then stirs several hours；Add equimolar Substituted cyclopentadienyl, and mixture stir more than 12 hours；Then with water hydrolysis reaction mixture, it is dried organic facies and steams Fall solvent, purified, filter, crystallize after obtain the ligand of substituted fluorene cyclopentadienyl group；B: fluorenyl and benzothienyl: will 3 is monosubstituted or 3, and 6-bis-substituted fluorene radical derivative is dissolved in ether and mixes with the hexane solution of n-BuLi, then stirs Several hours；Add equimolar benzothienyl, and mixture stirs more than 12 hours；Then mix with water hydrolysis Thing, is dried organic facies and also evaporates solvent, purified, filter, crystallize after obtain replacing the ligand of fluorenyl benzothienyl；C: fluorenes Base and indyl: by 3 monosubstituted or 3,6-bis-substituted fluorene radical derivative is dissolved in ether and with the hexane solution of n-BuLi Mixing, then stirs several hours；Add equimolar indole, and mixture stirs more than 12 hours；Then anti-with water hydrolysis Answer mixture, be dried organic facies and also evaporate solvent, purified, filter, crystallize after obtain replacing the ligand of fluorenyl indyl；d: Fluorenyl and 2,3,4,5-tetra-fluoro-1-methylindenyl: monosubstituted or 3 by 3,6-bis-substituted fluorene radical derivative be dissolved in ether and with The hexane solution mixing of n-BuLi, then stirs several hours；Add equimolar 2,3,4,5-tetra-fluoro-1-methylindenyl, and And mixture stirs more than 12 hours；Then with water hydrolysis reaction mixture, it is dried organic facies and evaporates solvent, purified, mistake Obtain replacing the ligand of the fluoro-1-methylindenyl of fluorenyl 2,3,4,5-tetra-after filter, crystallization.

The preparation method of synthetic lubricant base oil metallocene poly-alpha olefins catalyst the most according to claim 1 and 2, It is characterized in that: described step (3) substrate is to be during 5H-indeno [1,2-b] pyridine radicals: a:5H-indeno [1,2-b] pyridine radicals base And cyclopentadienyl group: 5H-indeno [1,2-b] pyridinium dissolution is mixed, then in ether and with the hexane solution of n-BuLi Stir several hours；Add equimolar substituted cyclopentadienyl, and mixture stirs more than 12 hours；Then anti-with water hydrolysis Answer mixture, be dried organic facies and also evaporate solvent, purified, filter, crystallize after obtain 5H-indeno [1,2-b] pyridyl ring penta The ligand of dialkylene；B:5H-indeno [1,2-b] pyridine radicals and benzothienyl: 5H-indeno [1,2-b] pyridinium dissolution is existed Mix in ether and with the hexane solution of n-BuLi, then stir several hours；Add equimolar benzothienyl, and mix Compound stirs more than 12 hours；Then with water hydrolysis reaction mixture, it is dried organic facies and also evaporates solvent, purified, filter, tie The ligand of 5H-indeno [1,2-b] pyridine radicals base benzothienyl is obtained after crystalline substance；C:5H-indeno [1,2-b] pyridine radicals and indole Base: 5H-indeno [1,2-b] pyridinyl derivatives be dissolved in ether and mix with the hexane solution of n-BuLi, then stirring Mix several hours；Add equimolar indole, and mixture stirs more than 12 hours；Then with water hydrolysis reaction mixture, dry Dry organic facies also evaporates solvent, purified, filter, crystallize after obtain the ligand of 5H-indeno [1,2-b] pyridine radicals indyl； D:5H-indeno [1,2-b] pyridine radicals and 2,3,4,5-tetra-fluoro-1-methylindenyl: by 5H-indeno [1,2-b] pyridinium dissolution in second Mix in ether and with the hexane solution of n-BuLi, then stir several hours；Add equimolar 2,3,4,5-tetra-fluoro-1-methyl Indenyl, and mixture stir more than 12 hours；Then with water hydrolysis reaction mixture, it is dried organic facies and evaporates solvent, warp Purification, filter, crystallize after obtain the ligand of the fluoro-1-methylindenyl of 5H-indeno [1,2-b] pyridine radicals 2,3,4,5-tetra-.

The preparation method of synthetic lubricant base oil metallocene poly-alpha olefins catalyst the most according to claim 1 and 2, It is characterized in that: described step (3) substrate is to be during 5H-indeno [1,2-b] thiopyranyl: a:5H-indeno [1,2-b] sulfur generation Pyranose and cyclopentadienyl group: 5H-indeno [1,2-b] thio-pyrylium is dissolved in ether and with the hexane solution of n-BuLi Mixing, then stirs several hours；Add equimolar substituted cyclopentadienyl, and mixture stirs more than 12 hours；Then With water hydrolysis reaction mixture, be dried organic facies and also evaporate solvent, purified, filter, crystallize after obtain 5H-indeno [1,2-b] The ligand of thio-pyrylium cyclopentadienyl group；B:5H-indeno [1,2-b] thiopyranyl and benzothienyl: by 5H-indeno [1,2-b] thio-pyrylium radical derivative is dissolved in ether and mixes with the hexane solution of n-BuLi, then stirs several hours； Add equimolar benzothienyl, and mixture stirs more than 12 hours；Then with water hydrolysis reaction mixture, it is dried and has Machine phase also evaporates solvent, purified, filter, crystallize after obtain replacing 5H-indeno [1,2-b] thiopyranyl benzothienyl Ligand；C:5H-indeno [1,2-b] thiopyranyl and indyl: 5H-indeno [1,2-b] thio-pyrylium is dissolved in ether In and mix with the hexane solution of n-BuLi, then stir several hours；Add equimolar indole, and mixture stirring 12 More than hour；Then with water hydrolysis reaction mixture, be dried organic facies and also evaporate solvent, purified, filter, crystallize after obtain The ligand of 5H-indeno [1,2-b] thiopyranyl；D:5H-indeno [1,2-b] thiopyranyl and 2,3,4,5-tetra-fluoro-1- Methylindenyl: 5H-indeno [1,2-b] thio-pyrylium radical derivative is dissolved in ether and mixed with the hexane solution of n-BuLi Close, then stir several hours；Add equimolar 2,3,4,5-tetra-fluoro-1-methylindenyl, and mixture stir 12 hours with On；Then with water hydrolysis reaction mixture, be dried organic facies and also evaporate solvent, purified, filter, crystallize after obtain 5H-indeno The ligand of the fluoro-1-methylindenyl of [1,2-b] thiopyranyl 2,3,4,5-tetra-.

The preparation method of synthetic lubricant base oil metallocene poly-alpha olefins catalyst the most according to claim 1 and 2, It is characterized in that: described step (4) is: ring-type silicon ether halogenide or substituted-phenyl halogenide are dissolved in ether, and to Wherein drip n-BuLi, then drip metal halide, after stirring the mixture at least 12 hours, add step (3) (4) (5) in, the ligand lithium salts of preparation, then through including extraction, distillation, purification, the post processing of crystallization, i.e. can get product catalyst Agent.

8. the metallocene poly-alpha olefins catalyst of the synthetic lubricant base oil as described in any one of Claims 1 to 5 Application, it is characterised in that: it is as the catalyst of synthetic lubricant base oil reaction, and during reaction, its addition is reaction-ure mixture 0.1～10ppm wt%.