CN108559012A

CN108559012A - Synthetic lubricant base oil metallocene poly-alpha olefins catalyst and its preparation and application

Info

Publication number: CN108559012A
Application number: CN201810287608.5A
Authority: CN
Inventors: 魏东初; 李兵
Original assignee: Abbott Science And Technology (hangzhou) Co Ltd
Current assignee: Abbott Science And Technology (hangzhou) Co Ltd
Priority date: 2015-01-26
Filing date: 2016-01-22
Publication date: 2018-09-21
Also published as: CN106046211A

Abstract

The present invention relates to a kind of synthetic lubricant base oil metallocene polyalphaolefin catalyst, its structure includes substituted aromatic base, bridge formation atom, unsubstituted or 3 is monosubstituted or 3, the 5H indenos [1 of 6 two substitutions, 2 b] pyridyl group or unsubstituted or 3 is monosubstituted or 3,5H indenos [1,2 b] thiopyranyl of 6 two substitutions, metal dentate.Metallocene polyalphaolefin catalyst of the present invention, stable structure, high catalytic efficiency, preparation method of the invention is easy to operate, yield is high, raw material is easy to get, at low cost, environmental pollution is small, is easy to industrialized production.

Description

Synthetic lubricant base oil metallocene poly-alpha olefins catalyst and its preparation and application

Technical field

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

Background technology

Poly alpha olefine synthetic oil (PAO) is a kind of lube base oil haveing excellent performance, and is current hybrid-engine oil, tooth Most widely used one of oil base stock, is greatly extended by the synthetic oil of its modulation in wheel oil and other iundustrial oils, fat Application range of the lubricant grease under high temperature, low temperature, high load capacity and other harsh conditions, provides excellent viscosity temperature characteristic, 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 the utilization rate and service life of equipment, is created for user abundant Economic benefit, while again environmental protection and energy saving aspect realize prodigious social benefit.Therefore, current many most high-grade PAO has generally been particularly preferred as the base oil of lubricating oil in lubricating oil product.

ExxonMobil companies are one of the dominant companies of produced worldwide poly alpha olefin, are proposed use in May, 2010 The high viscosity poly alpha olefin SpectraSyn Elite of new generation of metallocene catalyst synthesis technology synthesis, to be different from routine PAO, this new PAO base oils are referred to as mPAO.PAO molecules possess backbone outstanding under normal conditions, from backbone with unordered Mode stretches out side chain different in size.Its molecular structure can be shown such as following formula.And mPAO uses metallocene catalyst synthesis technology, Metallocene is single site catalysts, the available very uniform chemical products of unique geometry, so mPAO possesses Upright side chain is not present in pectinate texture.This shape possesses improved rheological behavior and flow performance compared with conventional PAO, So as to preferably provide shear stability, lower 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.These characteristics determine that mPAO's is answering for high severity using target With, including power drive system and gear oil, compressor lubricant oil, transmission fluid and industrial lubricant.

The external synthesis in relation to mPAO and exploitation starting are more early, 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 Japanese light extraction have been realized in industrialized production and are released to market in the recent period The product of oneself, concrete condition are as shown in table 1.The country is constantly in backward situation in terms of PAO synthesis, in recent years Shanghai Nanogram Corp. and Fu Ke lions company just complete the research and development of the PAO synthetic technologys with independent intellectual property right and have Related product It releases.But the rare relevant research of research and development and report, the at present research and development in this field in relation to mPAO are substantially at blank.

The performance of poly alpha olefine synthetic oil with polymer raw in addition to having outside the Pass, largely by its synthetic catalyst and conjunction It is determined at technique.Currently, the synthesis of mainstream PAO products mostly uses greatly non-single site catalysts, obtained product knot Structure is not neat, so compared with single active center's metallocene catalyst sintetics, there is a certain distance on viscosity temperature characteristic.It closes Mainly there are two major classes at the metallocene catalyst of mPAO：Non-bridged combined metal catalyst and means of special bridged metallocene catalysts.Using non- Product synthesized by means of special bridged metallocene catalysts is the PAO of middle low viscosity, and uses means of special bridged metallocene catalysts obtained then For the PAO of medium-high viscosity.

Invention content

The purpose of the present invention is：A kind of new structural synthetic lubricant base oil metallocene poly-alpha olefins catalysis is provided Agent and its preparation method and application, mainly with bridging silicon or carbon atom, 3 monosubstituted either 36 disubstituted fluorenyls or The transistion metal compound of 5H- indenos [1,2-b] pyridyl group or 5H- indenos [1,2-b] thiopyranyl.

On the one hand, the present invention provides a kind of new structural synthetic lubricant base oil metallocene poly-alpha olefins to be catalyzed Agent.

The synthetic lubricant base oil metallocene poly-alpha olefins catalyst structure includes substituted aromatic base, bridging original Sub, unsubstituted or 3 monosubstituted either 36 disubstituted fluorenyls are either unsubstituted or 5H- indenos [1 2-b] pyridyl group or Unsubstituted or 5H- indenos [1,2-b] thiopyranyl, metal dentate；The structural formula of the catalyst is：

Wherein：

Substituted aromatic base Ar is

X is N or S；

Y is bridge formation atom, is silicon or carbon；

R₁It is the substituent group on cyclopentadiene, is fluorine atom or hydrogen atom；R₂It is substituent group on benzothiophene, is that fluorine is former Son or hydrogen atom； R₃It is substituent group on indoles, is fluorine atom or hydrogen atom；

R₄It is the substituent group on bridge formation atom, is cyclohexyl, cyclopenta, cyclobutyl when bridge formation atom is silicon；Work as bridging When atom is carbon, for 1,3,5- tri- substitutions or monosubstituted disubstituted phenyl；

R₅It is described 3 monosubstituted or bis- substitutions of 3,6- fluorenyls or 3 monosubstituted or bis- substitutions of 3,6- 5H- indenos [1,2-b] pyridyl group is 3 monosubstituted or 3, and the substituent group on 5H- indenos [1,2-b] thiopyranyls of bis- substitutions of 6-, is halogen The alkyl of element or all straight chains of carbon atom number 2~24, branch；

M is metal zirconium or hafnium or titanium；

L is the halogen being coordinated with metal, different according to the price of metal, and halogen replaces number different.

Specific implementation mode according to the present invention, in the catalyst：

1) fluorenyl is one of the group in following groups：Fluorenyl, 3- fluorine fluorenyl, 3,6- difluoros fluorenyl, 3- bromines fluorenyl, 3,6- dibromo fluorenyls, 3- iodine fluorenyl, 3,6- diiodo-s fluorenyl, 3- ethylfluorenyls, 3,6- diethyl fluorenyl, 3- propyl fluorenyl, 3,6- Dipropyl fluorenyl, 3- butyl fluorenyl, 3,6- dibutylfluorenyls, 3- isopropyls fluorenyl, 3,6- diisopropyls fluorenyl, 3- isobutyl groups Fluorenyl, 3,6- diisobutyls fluorenyl, 3- amyls fluorenyl, 3,6- diamyl fluorenyl, 3- isopentyl fluorenyl, 3,6- diisoamyl fluorenes Base, 3- t-butyl fluorenyls, 3,6- di-t-butyls fluorenyl, 3- allyls fluorenyl, 3,6- diallyls fluorenyl, 3- hexyls fluorenyl, 3, 6- dihexyls fluorenyl, 3- isohesyls fluorenyl, 3,6-, bis- isohesyl fluorenyls, 3- t-butylethyls fluorenyl, 3,6- di-t-butyl ethyls Fluorenyl, 3- heptyl fluorenyl, 3,6- diheptyls fluorenyl, the different heptyl fluorenyls of 3-, 3,6-, bis- different heptyl fluorenyls, 3- tertiary butyl propyl fluorenes Base, 3,6- di-t-butyl propyl fluorenyl, 3- octyls fluorenyl, 3,6- dioctyls fluorenyl, 3- iso-octyl fluorenyl, 3,6- diisooctyl fluorenes Base, 3- tertiary butyl butyl fluorenyl, 3,6- di-t-butyl butyl fluorenyl, 3- undecyls fluorenyl, 3,6-, bis--undecyls fluorenyl, 3- dodecyls fluorenyl, 3,6-, bis--dodecyls fluorenyl, 3- tridecyls fluorenyl, 3,6-, bis--tridecyls fluorenyl, 3- 14 Alkyl fluorenyl, 3,6-, bis--myristyls fluorenyl, 3- pentadecyls fluorenyl, 3,6-, bis--pentadecyls fluorenyl, 3- cetyl fluorenes Base, 3,6-, bis--cetyls fluorenyl, 3- heptadecyls fluorenyl, 3,6-, bis--heptadecyls fluorenyl, 3- octadecyls fluorenyl, 3, Bis--octadecyls of 6- fluorenyl, 3- nonadecyls fluorenyl, 3,6-, bis--nonadecyls fluorenyl, 3- eicosyls fluorenyl, 3,6- bis-- Eicosyl fluorenyl, 3- heneicosyls fluorenyl, 3,6-, bis--heneicosyls fluorenyl, 3- docosyls fluorenyl, 3,6- bis-- Docosyl fluorenyl, 3- tricosyls fluorenyl, 3,6-, bis--tricosyls fluorenyl, 3- tetracosyls fluorenyl, 3,6- One of two-tetracosyl fluorenyls；

2) 5H- indenos [1,2-b] pyridyl group is one of the group in following groups：5H- indenos [1,2-b] pyridine Base, 3- fluorine 5H- indenos [1,2-b] pyridyl group, 3,6- difluoro 5H- indenos [1,2-b] pyridyl group, 3- bromine 5H- indenos [1,2-b] Pyridyl group, 3,6- dibromo 5H- indenos [1,2-b] pyridyl group, 3- iodine 5H- indenos [1,2-b] pyridyl group, 3,6- diiodo- 5H- indenos [1,2-b] pyridyl group, 3- ethyl 5H- indenos [1,2-b] pyridyl group, 3,6- diethyl 5H- indenos [1,2-b] pyridyl group, 3- third Base 5H- indenos [1,2-b] pyridyl group, 3,6- dipropyl 5H- indenos [1,2-b] pyridyl group, 3- butyl 5H- indenos [1,2-b] pyrrole Piperidinyl, 3,6- dibutyl 5H- indenos [1,2-b] pyridyl group, 3- isopropyl 5H- indenos [1,2-b] pyridyl group, 3,6- diisopropyls 5H- indenos [1,2-b] pyridyl group, 3- isobutyl group 5H- indenos [1,2-b] pyridyl group, 3,6- diisobutyl 5H- indenos [1,2-b] Pyridyl group, 3- amyl 5H- indenos [1,2-b] pyridyl group, 3,6- diamyl 5H- indenos [1,2-b] pyridyl group, 3- isopentyl 5H- Indeno [1,2-b] pyridyl group, 3,6- diisoamyl 5H- indenos [1,2-b] pyridyl group, 3- tertiary butyl 5H- indenos [1,2-b] pyrrole Piperidinyl, 3,6- di-t-butyl 5H- indenos [1,2-b] pyridyl group, 3- allyl 5H- indenos [1,2-b] pyridyl group, 3,6- diene Propyl 5H- indenos [1,2-b] pyridyl group, 3- hexyl 5H- indenos [1,2-b] pyridyl group, 3,6- dihexyl 5H- indenos [1,2-b] Pyridyl group, 3- isohesyl 5H- indenos [1,2-b] pyridyl group, 3,6- bis- isohesyl 5H- indenos [1,2-b] pyridyl group, 3- tertiary butyls Ethyl 5H- indenos [1,2-b] pyridyl group, 3,6- di-t-butyls ethyl 5H- indenos [1,2-b] pyridyl group, 3- heptyl 5H- indenos [1,2-b] pyridyl group, 3,6- diheptyl 5H- indenos [1,2-b] pyridyl group, different heptyl 5H- indenos [1, the 2-b] pyridyl groups of 3-, 3, Bis- different heptyl 5H- indenos [1,2-b] pyridyl groups of 6-, 3- tertiary butyls propyl 5H- indenos [1,2-b] pyridyl group, 3,6- di-t-butyls Propyl 5H- indenos [1,2-b] pyridyl group, 3- octyl 5H- indenos [1,2-b] pyridyl group, 3,6- dioctyl 5H- indenos [1,2-b] Pyridyl group, 3- iso-octyl 5H- indenos [1,2-b] pyridyl group, 3,6- diisooctyl 5H- indenos [1,2-b] pyridyl group, the tertiary fourths of 3- Base butyl 5H- indenos [1,2-b] pyridyl group, 3,6- di-t-butyls butyl 5H- indenos [1,2-b] pyridyl group, 3- undecyls 5H- Indeno [1,2-b] pyridyl group, 3,6- bis--undecyl 5H- indenos [1,2-b] pyridyl group, 3- dodecyl 5H- indenos [1,2- B] pyridyl group, 3,6- bis--dodecyl 5H- indenos [1,2-b] pyridyl group, 3- tridecyl 5H- indenos [1,2-b] pyridyl group, 3,6- bis--tridecyl 5H- indenos [1,2-b] pyridyl groups, 3- myristyl 5H- indenos [1,2-b] pyridyl group, 3,6- bis--ten Tetraalkyl 5H- indenos [1,2-b] pyridyl group, 3- pentadecyl 5H- indenos [1,2-b] pyridyl group, 3,6-, bis--pentadecyls 5H- Indeno [1,2-b] pyridyl group, 3- cetyl 5H- indenos [1,2-b] pyridyl group, 3,6-, bis--cetyl 5H- indenos [1,2- B] pyridyl group, 3- heptadecyl 5H- indenos [1,2-b] pyridyl group, 3,6- bis--heptadecyl 5H- indenos [1,2-b] pyridyl group, 3- octadecyl 5H- indenos [1,2-b] pyridyl group, 3,6- bis--octadecyl 5H- indenos [1,2-b] pyridyl group, 3- nonadecyls 5H- indenos [1,2-b] pyridyl group, 3,6- bis--nonadecyl 5H- indenos [1,2-b] pyridyl group, 3- eicosyl 5H- indenos [1, 2-b] pyridyl group, 3,6- bis--eicosyl 5H- indenos [1,2-b] pyridyl group, 3- heneicosyl 5H- indenos [1,2-b] pyrrole Piperidinyl, 3,6- bis--heneicosyl 5H- indenos [1,2-b] pyridyl group, 3- docosyl 5H- indenos [1,2-b] pyridyl group, 3,6- bis--docosyl 5H- indenos [1,2-b] pyridyl groups, 3- tricosyl 5H- indenos [1,2-b] pyridyl group, 3,6- Two-tricosyl 5H- indenos [1,2-b] pyridyl groups, 3- tetracosyl 5H- indenos [1,2-b] pyridyl group, 3,6- bis--two Myristyl 5H- indenos [1,2-b] pyridyl group；

3) 5H- indenos [1,2-b] thiopyranyl is one of the group in following groups:5H- indenos [1,2-b] sulphur For pyranose, 3- fluorine 5H- indenos [1,2-b] thiopyranyl, 3,6- difluoro 5H- indenos [1,2-b] thiopyranyl, 3- bromines 5H- indenos [1,2-b] thiopyranyl, 3,6- dibromo 5H- indenos [1,2-b] thiopyranyl, 3- iodine 5H- indenos [1,2-b] Thiopyranyl, 3,6- diiodo- 5H- indenos [1,2-b] thiopyranyl, 3- ethyl 5H- indenos [1,2-b] thiopyranyl, 3,6- diethyl 5H- indenos [1,2-b] thiopyranyls, 3- propyl 5H- indenos [1,2-b] thiopyranyl, 3,6- dipropyl 5H- indenos [1,2-b] thiopyranyl, 3- butyl 5H- indenos [1,2-b] thiopyranyl, 3,6- dibutyl 5H- indenos [1, 2-b] thiopyranyl, 3- isopropyl 5H- indenos [1,2-b] thiopyranyl, 3,6- diisopropyl 5H- indenos [1,2-b] sulphur For pyranose, 3- isobutyl group 5H- indenos [1,2-b] thiopyranyl, 3,6- diisobutyl 5H- indenos [1,2-b] thio-pyrylium Base, 3- amyl 5H- indenos [1,2-b] thiopyranyl, 3,6- diamyl 5H- indenos [1,2-b] thiopyranyl, 3- isoamyls Base 5H- indenos [1,2-b] thiopyranyl, 3,6- diisoamyl 5H- indenos [1,2-b] thiopyranyl, 3- tertiary butyls 5H- Indeno [1,2-b] thiopyranyl, 3,6- di-t-butyl 5H- indenos [1,2-b] thiopyranyl, 3- allyl 5H- indenos [1,2-b] thiopyranyl, 3,6- diallyl 5H- indenos [1,2-b] thiopyranyl, 3- hexyl 5H- indenos [1,2-b] sulphur For pyranose, 3,6- dihexyl 5H- indenos [1,2-b] thiopyranyl, 3- isohesyl 5H- indenos [1,2-b] thio-pyrylium Base, 3,6- bis- isohesyl 5H- indenos [1,2-b] thiopyranyl, 3- t-butylethyl 5H- indenos [1,2-b] thio-pyrylium Base, 3,6- di-t-butyls ethyl 5H- indenos [1,2-b] thiopyranyl, 3- heptyl 5H- indenos [1,2-b] thiopyranyl, 3,6- diheptyl 5H- indenos [1,2-b] thiopyranyls, different heptyl 5H- indenos [1, the 2-b] thiopyranyls of 3-, 3,6- bis- are different Heptyl 5H- indenos [1,2-b] thiopyranyl, 3- tertiary butyls propyl 5H- indenos [1,2-b] thiopyranyl, 3,6-, bis- tertiary fourths Base propyl 5H- indenos [1,2-b] thiopyranyl, 3- octyl 5H- indenos [1,2-b] thiopyranyl, 3,6- dioctyl 5H- indenes And [1,2-b] thiopyranyl, 3- iso-octyl 5H- indenos [1,2-b] thiopyranyl, 3,6- diisooctyl 5H- indenos [1,2- B] thiopyranyl, 3- tertiary butyls butyl 5H- indenos [1,2-b] thiopyranyl, 3,6- di-t-butyl butyl 5H- indenos [1, 2-b] thiopyranyl, 3- undecyl 5H- indenos [1,2-b] thiopyranyl, 3,6-, bis--undecyl 5H- indenos [1,2- B] thiopyranyl, 3- dodecyl 5H- indenos [1,2-b] thiopyranyl, 3,6-, bis--dodecyl 5H- indenos [1,2-b] Thiopyranyl, 3- tridecyl 5H- indenos [1,2-b] thiopyranyl, 3,6-, bis--tridecyl 5H- indenos [1,2-b] Thiopyranyl, 3- myristyl 5H- indenos [1,2-b] thiopyranyl, 3,6- bis--myristyl 5H- indenos [1,2-b] sulphur It is thio for pyranose, 3- pentadecyl 5H- indenos [1,2-b] thiopyranyl, 3,6-, bis--pentadecyl 5H- indenos [1,2-b] Pyranose, 3- cetyl 5H- indenos [1,2-b] thiopyranyl, 3,6-, bis--cetyl 5H- indenos [1,2-b] are thio Pyranose, 3- heptadecyl 5H- indenos [1,2-b] thiopyranyl, 3,6-, bis--heptadecyl 5H- indenos [1,2-b] are thio Pyranose, 3- octadecyl 5H- indenos [1,2-b] thiopyranyl, 3,6- bis--octadecyl 5H- indenos [1,2-b] thio pyrrole It mutters base, 3- nonadecyl 5H- indenos [1,2-b] thiopyranyl, 3,6- bis--nonadecyl 5H- indenos [1,2-b] thio-pyrylium Base, 3- eicosyl 5H- indenos [1,2-b] thiopyranyl, 3,6- bis--eicosyl 5H- indenos [1,2-b] thio-pyrylium Base, 3- heneicosyl 5H- indenos [1,2-b] thiopyranyl, 3,6-, bis--heneicosyl 5H- indenos [1,2-b] are thio Pyranose, 3- docosyl 5H- indenos [1,2-b] thiopyranyl, 3,6- bis--docosyl 5H- indenos [1,2-b] sulphur For pyranose, 3- tricosyl 5H- indenos [1,2-b] thiopyranyl, 3,6-, bis--tricosyl 5H- indenos [1,2- B] thiopyranyl, 3- tetracosyl 5H- indenos [1,2-b] thiopyranyl, 3,6-, bis--tetracosyl 5H- indenos [1,2-b] thiopyranyl.

On the other hand, the present invention provides the synthetic lubricant base oil preparations of metallocene poly-alpha olefins catalyst Method and application.

1. substrate includes fluorenyl, the preparation method and application of the catalyst：

1) substrate is fluorenyl, and when cyclopentadienyl group, including step (1) prepares 3 monosubstituted or 3, and 6- bis- replaces fluorenyl to derive Object；(2) substituted cyclopentadienyl is prepared；(3) substitution fluorenyl/cyclopentadienyl ligand lithium salts is prepared；(4) halogenated hexamethylene is prepared Then the bridging coordination metal compound of silylation or halogenated substituted-phenyl will replace fluorenyl/cyclopentadienyl ligand lithium salts Diethyl ether solution reacted with bridging coordination metal compound, to obtain corresponding metallocene poly-alpha olefins catalyst.

In the preparation method, it is preferable that the step (3) is：By the 3 monosubstituted or substitution fluorenyl derivatives of 3,6- bis- It is dissolved in ether and is mixed with the hexane solution of n-BuLi, then stir a few houres；Add equimolar substitution ring penta 2 Alkenyl, and mixture stirs 12 hours or more；Then with water hydrolysis reaction mixture, dry organic phase simultaneously evaporates solvent, passes through The ligand of substituted fluorene cyclopentadienyl group is obtained after purifying, filtering, crystallization.

In the preparation method, the preferably described step (4) is：Halogenated hexamethylene silane is dissolved in ether, and to its Middle dropwise addition n-BuLi, is then added dropwise metal halide, after stirring the mixture at least 12 hours, or halogenated substituted benzene is dissolved In ether, and n-BuLi is added dropwise thereto, metal halide is then added dropwise, after stirring the mixture at least 12 hours, adds The preparation substitution fluorenyl/cyclopentadienyl ligand lithium salts for entering step (3), then through including extraction, distillation, purifying, crystallization etc. The post-processing of step, you can obtain product catalyst.

The application of the catalyst includes：As the catalyst of synthetic lubricant base oil reaction, its addition when reaction For 0.1~10 ppm wt% of reaction-ure mixture, preferably 0.2ppm wt%, 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%.

2) substrate is fluorenyl, and when benzothienyl, including step (1) prepares 3 monosubstituted or 3, and 6- bis- replaces fluorenyl to derive Object；(2) substitution benzothienyl is prepared；(3) substitution fluorenyl/benzothienyl ligand lithium salts is prepared；(4) halogenated hexamethylene is prepared Then the bridging coordination metal compound of silylation or halogenated substituted-phenyl will replace fluorenyl/benzothienyl ligand lithium salts Diethyl ether solution reacted with cyclohexasilanyl coordination metal compound, to obtain corresponding metallocene poly-alpha olefins catalyst.

In the preparation method, the preferably described step (3) is：By 3 is monosubstituted or 3,6- bis- replaces fluorenyl derivative molten Solution mixes in ether and with the hexane solution of n-BuLi, then stirs a few houres；Add equimolar substitution benzothiophene Base, and mixture stirs 12 hours or more；Then with water hydrolysis reaction mixture, dry organic phase simultaneously evaporates solvent, through pure Change, filter, obtain the ligand of substitution fluorenyl benzothienyl after crystallization.

In the preparation method, the preferably described step (4) is：Halogenated hexamethylene silane is dissolved in ether, and to its Middle dropwise addition n-BuLi, is then added dropwise metal halide, after stirring the mixture at least 12 hours, or halogenated substituted benzene is dissolved In ether, and n-BuLi is added dropwise thereto, metal halide is then added dropwise, after stirring the mixture at least 12 hours, adds The preparation substitution fluorenyl/benzothienyl ligand lithium salts for entering step (3), then through including extraction, distillation, purifying, crystallization etc. The post-processing of step, you can obtain product catalyst.

The application of the catalyst includes：As the catalyst of synthetic lubricant base oil reaction, its addition when reaction For 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, and when indyl, including step (1) prepares 3 monosubstituted or 3, and 6- bis- replaces fluorenyl derivative； (2) substituted indolyl is prepared；(3) substitution fluorenyl/indyl ligand lithium salts is prepared；(4) halogenated cyclic silane polymerization of olefin using catalyst is prepared Then metallic compound will replace the diethyl ether solution and cyclohexasilanyl coordinating metal chemical combination of fluorenyl/indyl ligand lithium salts Object reacts, to obtain corresponding metallocene poly-alpha olefins catalyst.

In the preparation method, the preferably described step (3) is：By 3 is monosubstituted or 3,6- bis- replaces fluorenyl derivative molten Solution mixes in ether and with the hexane solution of n-BuLi, then stirs a few houres；Equimolar substituted indolyl is added, and And mixture stirs 12 hours or more；Then with water hydrolysis reaction mixture, dry organic phase simultaneously evaporates solvent, purified, mistake The ligand of substitution fluorenyl indyl is obtained after filter, crystallization.

In the preparation method, it is preferable that the step (4) is：Halogenated hexamethylene silane is dissolved in ether, and to N-BuLi is wherein added dropwise, metal halide is then added dropwise, after stirring the mixture at least 12 hours, or halogenated substituted benzene is molten N-BuLi is added dropwise in ether in solution thereto, and metal halide is then added dropwise, after stirring the mixture at least 12 hours, The preparation that step (3) is added replaces fluorenyl/indyl ligand lithium salts, then through including the steps such as extraction, distillation, purifying, crystallization Rapid post-processing, you can obtain product catalyst.

The application of the catalyst includes：As the catalyst of synthetic lubricant base oil reaction, its addition when reaction For 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%, 1.8ppm 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 fluorenyl, and when 2,3,4,5- tetra- fluoro- 1- methylindenyls, including step (1) prepares 3 monosubstituted or 3,6- bis- Replace fluorenyl derivative；(2) 2,3,4,5- tetra- fluoro- 1- methylindenyls of substitution are prepared；(3) it prepares and replaces fluorenyl/2,3,4,5- tetra- Fluoro- 1- methylindenyls ligand lithium salts；(4) halogenated cyclic silylation coordination metal compound is prepared, fluorenyl/2 then will be replaced, The diethyl ether solution of 3,4,5- tetra- fluoro- 1- methylindenyls ligand lithium salts is reacted with cyclohexasilanyl coordination metal compound, with To corresponding metallocene poly-alpha olefins catalyst.

In the preparation method, the preferably described step (3) is：By 3 is monosubstituted or 3,6- bis- replaces fluorenyl derivative molten Solution mixes in ether and with the hexane solution of n-BuLi, then stirs a few houres；Equimolar 2 are added, 3,4,5- tetra- is fluoro- 1- methylindenyls, and mixture stirs 12 hours or more；Then with water hydrolysis reaction mixture, dry organic phase simultaneously evaporates molten Agent obtains the ligand of substitution fluorenyl indyl after purified, filtering, crystallization.

In the preparation method, it is preferable that the step (4) is：Halogenated hexamethylene silane is dissolved in ether, and to N-BuLi is wherein added dropwise, metal halide is then added dropwise, after stirring the mixture at least 12 hours, or halogenated substituted benzene is molten N-BuLi is added dropwise in ether in solution thereto, and metal halide is then added dropwise, after stirring the mixture at least 12 hours, Be added step (3) preparation replace fluorenyl/2,3,4,5- tetra- fluoro- 1- methylindenyls ligand lithium salts, then through include extract, Distillation, purifying, crystallization and etc. post-processing, you can obtain product catalyst.

2. substrate includes 5H- indenos [1,2-b] pyridyl group, the preparation method and application of the catalyst.

1) substrate is 5H- indenos [1,2-b] pyridyl group, and when cyclopentadienyl group, including step (1) prepares substituted-cyclopentadienyl Base；(2) 5H- indenos [1,2-b] pyridyl group/cyclopentadienyl ligand lithium salts is prepared；(3) bridging coordinating metal chemical combination is prepared Then the diethyl ether solution of 5H- indenos [1,2-b] pyridyl group/cyclopentadienyl ligand lithium salts and cyclohexasilanyl are coordinated by object Metallic compound reacts, to obtain corresponding metallocene poly-alpha olefins catalyst.

In the preparation method, the preferably described step (3) is：5H- indenos [1,2-b] pyridinyl derivatives are dissolved in It is mixed in ether and with the hexane solution of n-BuLi, then stirs a few houres；Equimolar substituted cyclopentadienyl is added, and And mixture stirs 12 hours or more；Then with water hydrolysis reaction mixture, dry organic phase simultaneously evaporates solvent, purified, mistake The ligand of 5H- indenos [1,2-b] pyridyl ring pentadienyl is obtained after filter, crystallization.

In the preparation method, the preferably described step (4) is：Halogenated hexamethylene silane is dissolved in ether, and to its Middle dropwise addition n-BuLi, is then added dropwise metal halide, after stirring the mixture at least 12 hours, or halogenated substituted benzene is dissolved In ether, and n-BuLi is added dropwise thereto, metal halide is then added dropwise, after stirring the mixture at least 12 hours, adds Enter preparation 5H- indenos [1,2-b] pyridyl group/cyclopentadienyl ligand lithium salts of step (3), then through including extraction, steaming Evaporate, purify, crystallizing and etc. post-processing, you can obtain product catalyst.

2) substrate is 5H- indenos [1,2-b] pyridyl group, and when benzothienyl, including step (1) prepares substitution benzothiophene Base；(2) 5H- indenos [1,2-b] pyridyl group/benzothienyl ligand lithium salts is prepared；(3) bridging coordinating metal chemical combination is prepared Then the diethyl ether solution of 5H- indenos [1,2-b] pyridyl group/benzothienyl ligand lithium salts and cyclohexasilanyl are coordinated by object Metallic compound reacts, to obtain corresponding metallocene poly-alpha olefins catalyst.

In the preparation method, the preferably described step (3) is：In ether simultaneously by 5H- indenos [1,2-b] pyridinium dissolution It is mixed with the hexane solution of n-BuLi, then stirs a few houres；Add equimolar substitution benzothienyl, and mixture Stir 12 hours or more；Then with water hydrolysis reaction mixture, dry organic phase simultaneously evaporates solvent, after purified, filtering, crystallization Obtain the ligand of 5H- indenos [1,2-b] pyridine benzothienyl.

In the preparation method, the preferably described step (4) is：Halogenated hexamethylene silane is dissolved in ether, and to its Middle dropwise addition n-BuLi, is then added dropwise metal halide, after stirring the mixture at least 12 hours, or halogenated substituted benzene is dissolved In ether, and n-BuLi is added dropwise thereto, metal halide is then added dropwise, after stirring the mixture at least 12 hours, adds Enter preparation 5H- indenos [1,2-b] pyridyl group/benzothienyl ligand lithium salts of step (3), then through including extraction, steaming Evaporate, purify, crystallizing and etc. post-processing, you can obtain product catalyst.

The application of the catalyst includes：As the catalyst of synthetic lubricant base oil reaction, its addition when reaction For 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- indenos [1,2-b] pyridyl group, and when indyl, including step (1) prepares substituted indolyl；(2) it makes Standby 5H- indeno [1,2-b] pyridyl group/indyl ligand lithium salts；(3) halogenated cyclic silylation coordination metal compound is prepared, Then by the diethyl ether solution of 5H- indenos [1,2-b] pyridyl group/indyl ligand lithium salts and cyclohexasilanyl coordinating metal chemical combination Object reacts, to obtain corresponding metallocene poly-alpha olefins catalyst.

In the preparation method, the preferably described step (3) is：In ether simultaneously by 5H- indenos [1,2-b] pyridinium dissolution It is mixed with the hexane solution of n-BuLi, then stirs a few houres；Equimolar substituted indolyl is added, and mixture stirs 12 hours or more；Then with water hydrolysis reaction mixture, dry organic phase simultaneously evaporates solvent, is obtained after purified, filtering, crystallization Replace the ligand of 5H- indenos [1,2-b] pyridyl group indyl.

In the preparation method, the preferably described step (4) is：Halogenated hexamethylene silane is dissolved in ether, and to its Middle dropwise addition n-BuLi, is then added dropwise metal halide, after stirring the mixture at least 12 hours, or halogenated substituted benzene is dissolved In ether, and n-BuLi is added dropwise thereto, metal halide is then added dropwise, after stirring the mixture at least 12 hours, adds Enter preparation 5H- indenos [1,2-b] pyridyl group/indyl ligand lithium salts of step (3), then through including extraction, distilling, pure Change, crystallization and etc. post-processing, you can obtain product catalyst.

4) substrate is 5H- indenos [1,2-b] pyridyl group, when 2,3,4,5- tetra- fluoro- 1- methylindenyls, including step (1) system It is on the waiting list 2,3,4,5- tetra- fluoro- 1- methylindenyls of generation；(2) 5H- indenos [1,2-b] pyridyl group/2,3,4,5- tetra- fluoro- 1- first are prepared Base indenyl ligands lithium salts；(3) halogenated cyclic silylation coordination metal compound is prepared, it then will substitution 5H- indenos [1,2-b] Pyridyl group/2,3, diethyl ether solution and the cyclohexasilanyl coordination metal compound of 4,5- tetra- fluoro- 1- methylindenyls ligand lithium salts Reaction, to obtain corresponding metallocene poly-alpha olefins catalyst.

In the preparation method, the preferably described step (3) is：5H- indenos [1,2-b] pyridinyl derivatives are dissolved in It is mixed in ether and with the hexane solution of n-BuLi, then stirs a few houres；Add equimolar 2,3,4,5- tetra- fluoro- 1- first Base indenyl, and mixture stirs 12 hours or more；Then with water hydrolysis reaction mixture, dry organic phase simultaneously evaporates solvent, The ligand of 5H- indenos [1,2-b] pyridyl group indyl is obtained after purified, filtering, crystallization.

In the preparation method, the preferably described step (4) is：Halogenated hexamethylene silane is dissolved in ether, and to its Middle dropwise addition n-BuLi, is then added dropwise metal halide, after stirring the mixture at least 12 hours, or halogenated substituted benzene is dissolved In ether, and n-BuLi is added dropwise thereto, metal halide is then added dropwise, after stirring the mixture at least 12 hours, adds Enter preparation 5H- indenos [1,2-b] pyridyl group/2,3 of step (3), then 4,5- tetra- fluoro- 1- methylindenyls ligand lithium salts pass through Including extraction, distillation, purifying, crystallization and etc. post-processing, you can obtain product catalyst.

3. substrate includes 5H- indenos [1,2-b] thiopyranyl, the preparation method and application of the catalyst：

1) substrate is 5H- indenos [1,2-b] thiopyranyl, and when cyclopentadienyl group, including step (1) prepares substitution ring penta Dialkylene；(2) 5H- indenos [1,2-b] thiopyranyl/cyclopentadienyl ligand lithium salts is prepared；(3) halogenated hexamethylene is prepared Silylation coordination metal compound, then by the second of 5H- indenos [1,2-b] thiopyranyl/cyclopentadienyl ligand lithium salts Ethereal solution is reacted with cyclohexasilanyl coordination metal compound, to obtain corresponding metallocene poly-alpha olefins catalyst.

In the preparation method, the preferably described step (3) is：5H- indenos [1,2-b] thio-pyrylium is dissolved in ether In and mix with the hexane solution of n-BuLi, then stir a few houres；Equimolar substituted cyclopentadienyl is added, and is mixed Object is closed to stir 12 hours or more；Then with water hydrolysis reaction mixture, dry organic phase simultaneously evaporates solvent, purified, filtering, knot The ligand of 5H- indenos [1,2-b] thio-pyrylium cyclopentadienyl group is obtained after crystalline substance.

In the preparation method, the preferably described step (4) is：Halogenated hexamethylene silane is dissolved in ether, and to its Middle dropwise addition n-BuLi, is then added dropwise metal halide, after stirring the mixture at least 12 hours, or halogenated substituted benzene is dissolved In ether, and n-BuLi is added dropwise thereto, metal halide is then added dropwise, after stirring the mixture at least 12 hours, adds Enter preparation 5H- indenos [1,2-b] thiopyranyl/cyclopentadienyl ligand lithium salts of step (3), then through include extract, Distillation, purifying, crystallization and etc. post-processing, you can obtain product catalyst.

2) substrate is 5H- indenos [1,2-b] thiopyranyl, and when benzothienyl, including step (1) prepares substitution benzo Thienyl；(2) 5H- indenos [1,2-b] thiopyranyl/benzothienyl ligand lithium salts is prepared；(3) halogenated cyclic is prepared Silylation coordination metal compound, then by the second of 5H- indenos [1,2-b] thiopyranyl/benzothienyl ligand lithium salts Ethereal solution is reacted with cyclohexasilanyl coordination metal compound, to obtain corresponding metallocene poly-alpha olefins catalyst.

In the preparation method, the preferably described step (3) is：5H- indenos [1,2-b] thio-pyrylium radical derivative is molten Solution mixes in ether and with the hexane solution of n-BuLi, then stirs a few houres；Add equimolar substitution benzothiophene Base, and mixture stirs 12 hours or more；Then with water hydrolysis reaction mixture, dry organic phase simultaneously evaporates solvent, through pure Change, filter, obtain the ligand of 5H- indenos [1,2-b] thiopyranyl benzothienyl after crystallization.

In the preparation method, the preferably described step (4) is：Halogenated hexamethylene silane is dissolved in ether, and to its Middle dropwise addition n-BuLi, is then added dropwise metal halide, after stirring the mixture at least 12 hours, or halogenated substituted benzene is dissolved In ether, and n-BuLi is added dropwise thereto, metal halide is then added dropwise, after stirring the mixture at least 12 hours, adds Enter preparation 5H- indenos [1,2-b] thiopyranyl/benzothienyl ligand lithium salts of step (3), then through include extract, Distillation, purifying, crystallization and etc. post-processing, you can obtain product catalyst.

3) substrate is 5H- indenos [1,2-b] thiopyranyl, and when indyl, including step (1) prepares substituted indolyl； (2) substitution 5H- indenos [1,2-b] thiopyranyl/indyl ligand lithium salts is prepared；(3) halogenated cyclic silylation is prepared to match Position metallic compound, then by the diethyl ether solution and hexamethylene of 5H- indenos [1,2-b] thiopyranyl/indyl ligand lithium salts Silylation coordination metal compound reacts, to obtain corresponding metallocene poly-alpha olefins catalyst.

In the preparation method, the preferably described step (3) is：5H- indenos [1,2-b] thio-pyrylium is dissolved in ether In and mix with the hexane solution of n-BuLi, then stir a few houres；Add equimolar substituted indolyl, and mixture Stir 12 hours or more；Then with water hydrolysis reaction mixture, dry organic phase simultaneously evaporates solvent, after purified, filtering, crystallization Obtain the ligand of 5H- indenos [1,2-b] thio-pyrylium indyl.

In the preparation method, the preferably described step (4) is：Halogenated hexamethylene silane is dissolved in ether, and to its Middle dropwise addition n-BuLi, is then added dropwise metal halide, after stirring the mixture at least 12 hours, or halogenated substituted benzene is dissolved In ether, and n-BuLi is added dropwise thereto, metal halide is then added dropwise, after stirring the mixture at least 12 hours, adds Enter preparation 5H- indenos [1,2-b] thiopyranyl/indyl ligand lithium salts of step (3), then through include extraction, distill, Purifying, crystallization and etc. post-processing, you can obtain product catalyst.

4) substrate is 5H- indenos [1,2-b] thiopyranyl, when 2,3,4,5- tetra- fluoro- 1- methylindenyls, including step (1) 2,3,4,5- tetra- fluoro- 1- methylindenyls of substitution are prepared；(2) 5H- indenos [1,2-b] thiopyranyl/2,3,4,5- tetra- is fluoro- 1- methylindenyl ligand lithium salts；(3) halogenated cyclic silylation coordination metal compound is prepared, then by 5H- indenos [1,2-b] Thiopyranyl/2,3, diethyl ether solution and the cyclohexasilanyl coordination metal of 4,5- tetra- fluoro- 1- methylindenyls ligand lithium salts Object reaction is closed, to obtain corresponding metallocene poly-alpha olefins catalyst.

In the preparation method, the preferably described step (3) is：5H- indenos [1,2-b] thio-pyrylium radical derivative is molten Solution mixes in ether and with the hexane solution of n-BuLi, then stirs a few houres；Equimolar 2 are added, 3,4,5- tetra- is fluoro- 1- methylindenyls, and mixture stirs 12 hours or more；Then with water hydrolysis reaction mixture, dry organic phase simultaneously evaporates Solvent obtains the ligand of 5H- indenos [1,2-b] thiopyranyl indyl after purified, filtering, crystallization.

In the preparation method, the preferably described step (4) is：Halogenated hexamethylene silane is dissolved in ether, and to its Middle dropwise addition n-BuLi, is then added dropwise metal halide, after stirring the mixture at least 12 hours, or halogenated substituted benzene is dissolved In ether, and n-BuLi is added dropwise thereto, metal halide is then added dropwise, after stirring the mixture at least 12 hours, adds Enter preparation 5H- indenos [1,2-b] thiopyranyl/2,3 of step (3), 4,5- tetra- fluoro- 1- methylindenyls ligand lithium salts, so By including extraction, distillation, purifying, crystallization and etc. post-processing, you can obtain product catalyst.

The application of the catalyst includes：As the catalyst of synthetic lubricant base oil reaction, its addition when reaction For 0.1~10 ppm wt% of reaction-ure mixture, preferably 0.2ppm wt%, 0.5ppm wt%, 0.6ppm wt%, 0.8ppm Wt%, 1.0ppm wt%, 1.3ppm wt%, 1.5 ppm 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%.

The present invention has the effect of positive：Synthetic lubricant base oil disclosed by the invention is catalyzed with metallocene poly alpha olefin Agent is compared with existing disclosed mPAO, and advantage is stable structure, high catalytic efficiency.Preparation method of the invention is easy to operate, produces Rate is high, raw material is easy to get, at low cost, environmental pollution is small, is easy to industrialized production.

Specific implementation mode

(embodiment 1) 3- fluorine substituted fluorenes are the zirconium metal catalyzer of ligand carbon bridging

(1) synthesis of 3- fluorine substituted fluorene.

9-Fluorenone (1.8g, 10mmol) and water (70mL) are added in reactor, stirred, heating, when temperature rises to 80- Start mixed acid (nitric acid and sulfuric acid 4 that nitric acid and sulfuric acid is added dropwise at 90 DEG C：7 mixing) 108 grams, flow back it is lower react 2.5-4h, add Water quenching is gone out reaction, is filtered, and obtained solid methanol and glacial acetic acid are recrystallized to give 3- nitros -9-Fluorenone (1.87g, 83% receive Rate).Feature：¹H NMR(CHCl₃d³)δppm: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- nitros -9-Fluorenone (1.87g) and ethyl alcohol are added to by weight 1: 50 in reactor, iron powder is added (465mg) is stirred, and is heated to reflux, and overnight, TLC detection raw material nitro compound fluorenes has disappeared for reaction.It is cooling, it is filtered to remove solid Body is evaporated solution.Ethyl acetate 100mL dissolvings are added, organic phase is washed 3 times with saturated salt solution 100mL, is merged organic phase, is done It filters and is evaporated after drying prescription drying.It is yellowish more than 97% 3- amino 9-Fluorenones that ethyl acetate petroleum ether recrystallization can be obtained purity Color solid (1.54g, 95%).Feature：¹H NMR(CHCl₃d³) δppm: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)。

3- amino 9-Fluorenone (1.54g) and 37% concentrated hydrochloric acid 50mL are mixed into postcooling to 0~5 DEG C, are added while stirring 35% sodium nitrite in aqueous solution 30mL reacts 1~1.5 hour between maintaining the temperature at 0~5 DEG C.Then it is slowly added dropwise 40% Fluoboric acid 20mL, viscosity increases during dropwise addition, filters, is filtered dry, then dried after stirring 15min after being added dropwise.It will Diazonium borofluoride is put into the four-hole bottle of another drying, and cracking reaction is carried out, and slow heating starts white cigarette of emerging in 50V Afterwards, electric jacket is removed, is heated again after waiting mitigation, for temperature in 130 V or so reaction time longests, finally heated to 200 DEG C straight It is steamed to no grease, then uses steam distillation instead.Oil reservoir is separated, water layer is extracted 2 times with 30ml toluene, is merged organic layer, is subtracted Until solvent-free steam, the mass percentage that the fluoro- 9-Fluorenones of 3- are measured through gas-chromatography area normalization method is for pressure distillation 99.6%, yield is up to 80.5%.Product is the fluoro- 9-Fluorenone 1.25g of 3-.Feature：¹H NMR(CHCl₃d³)δppm:8.44(m,1 H, 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).

5min is mixed in 615mg zinc powders, 300mg mercury chloride, 10ml concentrated hydrochloric acids and 40ml water, is stood.Incline aqueous, 95% ethyl alcohol of 40ml is added, the fluoro- 9-Fluorenones of 1.25g 3- are added, the dense salt of 30ml is added portionwise in reaction process in back flow reaction 8h Acid, it is cooling after hardening, it filters, crude product ethyl alcohol recrystallization, white solid product 3- fluorine substituted fluorenes is obtained after dry 0.93g.Feature：¹H NMR(CHCl₃d³)δppm:7.55 (m, 3H, aromatic ring H) 7.87 (m, 1H, aromatic ring H), 7.38 (m, 2H, virtues Ring 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 ethyl alcohol.Then the first of 10mmol is added Benzophenone.Then 20mmol 2- fluorine cyclopentadiene is added dropwise, mixture stirs 15 hours under reflux.Obtained product is then with water It dilutes and with extraction into heptane, evaporates organic phase, after excessive 2- fluorine cyclopentadienyl group is removed in distillation, after being extracted with ethyl acetate, Dry, filtering is evaporated.

(3) 10mmol 3- fluorine fluorenes is dissolved in 50ml ether and is mixed with the 1.6M hexane solutions of 10mmol n-BuLis, Then a few houres are stirred.Equimolar substitution 2- fluorine cyclopentadiene is added, and mixture is stirred overnight.Then with 50ml water water Reaction mixture is solved, organic phase is dried with sodium sulphate and evaporates solvent under vacuum, it is spare.

(4) the 1 of 20mmol, 3,5- trifluoro-benzenes are dissolved in 50mL ether, are cooled to -78 DEG C, and the butyl lithium of 20mmol is added dropwise, The zirconium chloride that 1eq is added after adding is gone back after mixture is stirred overnight, 10mmol ligands is added dropwise and are dissolved in 30ml ether Mixed liquor.After being added dropwise, mixture is stirred overnight, and is then evaporated solvent and with dichloromethane extracted residues, is merged organic Phase, dried over sodium sulfate, filtering then evaporates solvent under vacuum.In order to purify, residue is dissolved in pentane, solution warp Silica gel filters and crystallization can be obtained corresponding-two -1,3,5- trifluorophenyl-two of 3- fluorine fluorenes -2- fluorine cyclopentadiene at -30 DEG C Zirconium chloride.Feature：¹H NMR(DMSO d⁶)δppm: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 2) 3,6- difluoro substituted fluorenes are the zirconium metal catalyzer of ligand carbon bridging

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

9-Fluorenone (1.8g, 10mmol) and water are added to by weight 1: 7 in reactor, stirred, heating, when temperature liter Start mixed acid (nitric acid and sulfuric acid 8 that nitric acid and sulfuric acid is added dropwise when to 80-90 DEG C：2 mixing) 108 grams, the lower reaction 20 that flows back is small When, add water quenching to go out reaction, filters, obtained solid methanol and glacial acetic acid recrystallization, dry 3,6- dinitros -9-Fluorenone (1.35g, 50%).Feature：¹H NMR(CHCl₃d³) δppm: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 ethyl alcohol are added to by weight 1: 5 in reactor, and iron powder is added (2mmol) is stirred, and is heated to reflux, and overnight, TLC detection raw material nitro compound fluorenes has disappeared for reaction.It is cooling, it is filtered to remove solid Body is evaporated solution.Ethyl acetate 100mL dissolvings are added, organic phase is washed 3 times with saturated salt solution 100mL, is merged organic phase, is done It filters and is evaporated after drying prescription drying.Ethyl acetate petroleum ether recrystallization can be obtained 3, the 6- diamino 9-Fluorenones that purity is more than 97% Faint yellow solid (0.95g, 90%).Feature：¹H NMR (CHCl₃d³)δppm: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)。

3,6- diamino 9-Fluorenone (950mg) and 37% concentrated hydrochloric acid are mixed into postcooling to 0~5 DEG C, are added while stirring 35% sodium nitrite in aqueous solution reacts 1~1.5 hour between maintaining the temperature at 0~5 DEG C.Then 40% fluorine boron is slowly added dropwise Acid, viscosity increases during dropwise addition, filters, is filtered dry, then dried after stirring 15min after being added dropwise.By diazonium fluoride boron Hydrochlorate is put into the four-hole bottle of another drying, and cracking reaction is carried out, and slow heating removes electricity after 50V starts to emerge white cigarette Hot jacket heats again after waiting mitigation, temperature in 130V or so reaction time longests, it is finally heated to 200 DEG C up to no grease It steams, then uses steam distillation instead.Separate oil reservoir, water layer is extracted 2 times with 30ml toluene, merges organic layer, vacuum distillation until Solvent-free to steam, the mass percentage that 3,6-, bis- fluoro- 9-Fluorenones are measured through gas-chromatography area normalization method is 99.6%, yield Up to 80.5%.Product is 3,6-, bis- fluoro- 9-Fluorenones (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).

5min is mixed in 3.15g zinc powders, 1.5g mercury chloride, 10ml concentrated hydrochloric acids and 20ml water, is stood.Incline aqueous, 95% ethyl alcohol of 20ml is added, 700mg 3, bis- fluoro- 9-Fluorenones of 6- is added, 15ml is added portionwise in reaction process in back flow reaction 8h Concentrated hydrochloric acid, it is cooling after hardening, it filters, crude product ethyl alcohol recrystallization, obtains white solid product 3 after dry, 6- difluoros take For fluorenes 523mg.Feature：¹H NMR(CHCl₃d³) δppm: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 1 step of embodiment (2).

(3) 10mmol 3,6- difluoros fluorenes is dissolved in the 1.6M hexane solutions in 50ml ether and with 10mmol n-BuLis Mixing, then stirs a few houres.It adds equimolar 2- fluorine cyclopentadienyl group (being same as above) and mixture is stirred overnight.Then with 50ml water hydrolysis reaction mixtures dry organic phase with sodium sulphate and evaporate solvent under vacuum, spare.

(4) the 1 of 20mmol, 3,5- trifluoro-benzenes are dissolved in 50mL ether, are cooled to -78 DEG C, and the butyl lithium of 20mmol is added dropwise, The zirconium chloride that 1eq is added after adding is gone back after mixture is stirred overnight, 10mmol ligands is added dropwise and are dissolved in 30ml ether Mixed liquor.After being added dropwise, mixture is stirred overnight, and is then evaporated solvent and with dichloromethane extracted residues, is merged organic Phase, dried over sodium sulfate, filtering then evaporates solvent under vacuum.In order to purify, residue is dissolved in pentane, solution warp Silica gel filters and crystallization can be obtained corresponding-two -1,3,5- trifluoro-benzene of 3,6- difluoros fluorenes -2- fluorine cyclopentadiene at -30 DEG C Base-zirconium dichloride.Feature：¹H NMR(DMSO d⁶)δppm:7.55 (m, 4 H, 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 fluorenes are the zirconium metal catalyzer of ligand carbon bridging

(1) synthesis of 3- ethyls substituted fluorene.

9-Fluorenone (1.8g, 10mmol) and water are added to by weight 1: 7 in reactor, stirred, heating, when temperature liter Start mixed acid (nitric acid and sulfuric acid 8 that nitric acid and sulfuric acid is added dropwise when to 80-90 DEG C：2 mixing) 108 grams, the lower reaction 20 that flows back is small When, add water quenching to go out reaction, filters, obtained solid methanol and glacial acetic acid recrystallization, dry 3- nitros -9-Fluorenone (1.35g, 50%).Feature：¹H NMR(CHCl₃d³)δppm:8.75 (s, 1H, aromatic ring H) 8.44 (m, 1H, aromatic ring H), 8.34 (m, 1H, virtues Ring 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- nitros -9-Fluorenone (1.35g) and ethyl alcohol are added to by weight 1: 5 in reactor, iron powder (2mmol) is added Stirring, is heated to reflux, and overnight, TLC detection raw material nitro compound fluorenes has disappeared for reaction.It is cooling, it is filtered to remove solid, is evaporated Solution.Ethyl acetate 100 mL dissolvings are added, organic phase is washed 3 times with saturated salt solution 100mL, merges organic phase, and drier is dry Filtering is evaporated after dry.Ethyl acetate petroleum ether recrystallization can be obtained the 3- amino 9-Fluorenone faint yellow solids that purity is more than 97% (0.95g, 90%).Feature：¹H NMR(CHCl₃d³) δppm: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, virtues Ring H), 6.27 (m, 2H, NH₂)。

3- amino 9-Fluorenone (1.95g) and 37% concentrated hydrochloric acid are mixed into postcooling to 0~5 DEG C, 35% is added while stirring Sodium nitrite in aqueous solution is maintained the temperature between O~5 DEG C and is reacted 1~1.5 hour.Then hydrobromic acid is slowly added dropwise, is added dropwise The protobromide ketone of catalytic amount is added afterwards, is warming up to after room temperature and is warming up to 50 DEG C of two hours of reaction again.TLC display reactions finish. Stop reaction.It is filtered to remove solid.Ethyl acetate extraction 100mL is added and carries out extraction 3 times.Merge organic phase.Desiccant dryness Afterwards, it is filtered to remove drier.It is evaporated.Crude product ethyl acetate and petroleum ether, which carry out recrystallization, can obtain the bromo- 9-Fluorenones of white 3- Solid (2.33g, 90%).Feature：¹H NMR(CHCl₃d³)δppm:8.44 (m, 1 H, 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).

5min is mixed in 877mg zinc powders, 405mg mercury chloride, 20ml concentrated hydrochloric acids and 40ml water, is stood.Incline aqueous, 95% ethyl alcohol of 40ml is added, the bromo- 9-Fluorenones of 2.33g 3- are added, the dense salt of 30ml is added portionwise in reaction process in back flow reaction 8h Acid, it is cooling after hardening, it filters, crude product ethyl alcohol recrystallization, white solid product 3- bromine substituted fluorenes is obtained after dry 1.87g, yield 85%.Feature：¹H NMR(CHCl₃ d³)δppm: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 solids (1.87g) are dissolved in 50 milliliters of anhydrous tetrahydro furans, the magnesium powder 200mg of 1.1 equivalents is added and are urged The iodine of change amount, heating, cooling reaction continues heating reaction 2 hours after causing after, the tetrahydrofuran that grignard reagent is obtained by filtration is molten Liquid.It is cooled to 0 DEG C -5 DEG C of interior temperature, the solution of bromic ether is then added dropwise.Room temperature reaction 4 hours is warming up to after being added dropwise again.TLC Display reaction is complete.Aqueous ammonium chloride solution is slowly added dropwise, reaction is quenched.It is extracted 3 times, is associated with 25 milliliters of ethyl acetate Machine phase.After organic phase desiccant dryness, it is filtered to remove drier.Solvent evaporated.Crude product ethyl acetate and petroleum ether weight Crystallization.It can be obtained white 3- ethyls 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 1 step of embodiment (2)

(3) it is mixed to be dissolved in the 1.6M hexane solutions in 50ml ether and with 10mmol n-BuLis for 10mmol 3- ethyls fluorenes It closes, then stirs a few houres.Equimolar substitution 2- fluorine cyclopentadiene is added, and mixture is stirred overnight.Then with 50ml Water hydrolysis reaction mixture dries organic phase with sodium sulphate and evaporates solvent under vacuum, spare.

(4) the 1 of 20mmol, 3,5- trifluoro-benzenes are dissolved in 50mL ether, are cooled to -78 DEG C, and the butyl lithium of 20mmol is added dropwise, The zirconium chloride that 1eq is added after adding is gone back after mixture is stirred overnight, 10mmol ligands is added dropwise and are dissolved in 30ml ether Mixed liquor.After being added dropwise, mixture is stirred overnight, and is then evaporated solvent and with dichloromethane extracted residues, is merged organic Phase, dried over sodium sulfate, filtering then evaporates solvent under vacuum.In order to purify, residue is dissolved in pentane, solution warp Silica gel filters and crystallization can be obtained corresponding-two -1,3,5- trifluorophenyl of 3- ethyls fluorenes -2- fluorine cyclopentadiene-at -30 DEG C Zirconium dichloride.Feature：¹H NMR(DMSO d⁶)δppm: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), 2.60 (m, 2H, CH₂),1.25(m,3H,CH₃).(embodiment 4) 3- fluorine takes For the titanium metal catalyst that fluorenes is ligand carbon bridging

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

(4) the 1 of 20mmol, 3,5- trifluoro-benzenes are dissolved in 50mL ether, are cooled to -78 DEG C, and the butyl lithium of 20mmol is added dropwise, The titanium tetrachloride that 1eq is added after adding is gone back after mixture is stirred overnight, 10mmol ligands is added dropwise and are dissolved in 30ml ether Mixed liquor.After being added dropwise, mixture is stirred overnight, and is then evaporated solvent and with dichloromethane extracted residues, is merged organic Phase, dried over sodium sulfate, filtering then evaporates solvent under vacuum.In order to purify, residue is dissolved in pentane, solution warp Silica gel filters and crystallization can be obtained corresponding-two -1,3,5- trifluorophenyl-two of 3- fluorine fluorenes -2- fluorine cyclopentadiene at -30 DEG C Titanium chloride.Feature：¹H NMR(DMSO d⁶)δppm: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 5) 3,6- difluoro substituted fluorenes are the titanium metal catalyst of ligand carbon bridging

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

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

(4) the 1 of 20mmol, 3,5- trifluoro-benzenes are dissolved in 50mL ether, are cooled to -78 DEG C, and the butyl lithium of 20mmol is added dropwise, The titanium tetrachloride that 1eq is added after adding is gone back after mixture is stirred overnight, 10mmol ligands is added dropwise and are dissolved in 30ml ether Mixed liquor.After being added dropwise, mixture is stirred overnight, and is then evaporated solvent and with dichloromethane extracted residues, is merged organic Phase, dried over sodium sulfate, filtering then evaporates solvent under vacuum.In order to purify, residue is dissolved in pentane, solution warp Silica gel filters and crystallization can be obtained corresponding-two -1,3,5- trifluoro-benzene of 3,6- difluoros fluorenes -2- fluorine cyclopentadiene at -30 DEG C Base-titanium chloride.Feature：¹H NMR(DMSO d⁶)δppm:7.55 (m, 4 H, 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 fluorenes are the titanium metal catalyst of ligand carbon bridging

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

(4) the 1 of 20mmol, 3,5- trifluoro-benzenes are dissolved in 50mL ether, are cooled to -78 DEG C, and the butyl lithium of 20mmol is added dropwise, The titanium tetrachloride that 1eq is added after adding is gone back after mixture is stirred overnight, 10mmol ligands is added dropwise and are dissolved in 30ml ether Mixed liquor.After being added dropwise, mixture is stirred overnight, and is then evaporated solvent and with dichloromethane extracted residues, is merged organic Phase, dried over sodium sulfate, filtering then evaporates solvent under vacuum.In order to purify, residue is dissolved in pentane, solution warp Silica gel filters and crystallization can be obtained corresponding-two -1,3,5- trifluorophenyl of 3- ethyls fluorenes -2- fluorine cyclopentadiene-at -30 DEG C Titanium chloride.Feature：¹H NMR(DMSO d⁶)δppm: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), 2.60 (m, 2H, CH₂),1.25(m,3H,CH₃).(embodiment 7) 3- fluorine replaces Fluorenes is the hafnium metallic catalyst of ligand carbon bridging

(4) the 1 of 20mmol, 3,5- trifluoro-benzenes are dissolved in 50mL ether, are cooled to -78 DEG C, and the butyl lithium of 20mmol is added dropwise, The hafnium tetrachloride that 1eq is added after adding is gone back after mixture is stirred overnight, 10mmol ligands is added dropwise and are dissolved in 30ml ether Mixed liquor.After being added dropwise, mixture is stirred overnight, and is then evaporated solvent and with dichloromethane extracted residues, is merged organic Phase, dried over sodium sulfate, filtering then evaporates solvent under vacuum.In order to purify, residue is dissolved in pentane, solution warp Silica gel filters and crystallization can be obtained corresponding-two -1,3,5- trifluorophenyl-two of 3- fluorine fluorenes -2- fluorine cyclopentadiene at -30 DEG C Hafnium chloride.Feature：¹H NMR(DMSO d⁶)δppm: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 fluorenes are the hafnium metallic catalyst of ligand carbon bridging

(4) the 1 of 20mmol, 3,5- trifluoro-benzenes are dissolved in 50mL ether, are cooled to -78 DEG C, and the butyl lithium of 20mmol is added dropwise, The hafnium tetrachloride that 1eq is added after adding is gone back after mixture is stirred overnight, 10mmol ligands is added dropwise and are dissolved in 30ml ether Mixed liquor.After being added dropwise, mixture is stirred overnight, and is then evaporated solvent and with dichloromethane extracted residues, is merged organic Phase, dried over sodium sulfate, filtering then evaporates solvent under vacuum.In order to purify, residue is dissolved in pentane, solution warp Silica gel filters and crystallization can be obtained corresponding-two -1,3,5- trifluoro-benzene of 3,6- difluoros fluorenes -2- fluorine cyclopentadiene at -30 DEG C Base-hafnium dichloride.Feature：¹H NMR(DMSO d⁶)δppm:7.55 (m, 4 H, 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 fluorenes are the hafnium metallic catalyst of ligand carbon bridging

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

(4) the 1 of 20mmol, 3,5- trifluoro-benzenes are dissolved in 50mL ether, are cooled to -78 DEG C, and the butyl lithium of 20mmol is added dropwise, The hafnium tetrachloride that 1eq is added after adding is gone back after mixture is stirred overnight, 10mmol ligands is added dropwise and are dissolved in 30ml ether Mixed liquor.After being added dropwise, mixture is stirred overnight, and is then evaporated solvent and with dichloromethane extracted residues, is merged organic Phase, dried over sodium sulfate, filtering then evaporates solvent under vacuum.In order to purify, residue is dissolved in pentane, solution warp Silica gel filters and crystallization can be obtained corresponding-two -1,3,5- trifluorophenyl of 3- ethyls fluorenes -2- fluorine cyclopentadiene-at -30 DEG C Hafnium dichloride.Feature：¹H NMR(DMSO d⁶)δppm: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), 2.60 (m, 2H, CH₂),1.25(m,3H,CH₃).(embodiment 10) 3- fluorine takes It is the zirconium metal catalyzer of ligand silicon bridge even for fluorenes

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

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

(4) the cyclohexyl methyl chlorosilane of 20mmol is dissolved in 50mL ether, is cooled to -78 DEG C, and the fourth of 20mmol is added dropwise Base lithium adds the zirconium chloride of 1eq after adding, go back after mixture is stirred overnight, 10mmol ligands are added dropwise and are dissolved in 30ml second Mixed liquor in ether.After being added dropwise, mixture is stirred overnight, and is then evaporated solvent and with dichloromethane extracted residues, is closed And organic phase, dried over sodium sulfate, filtering then evaporates solvent under vacuum.In order to purify, residue is dissolved in pentane, Solution is filtered through silica gel and crystallization can be obtained corresponding 3- fluorine fluorenes -2- fluorine cyclopentadiene-cyclohexyl methyl silicon-two at -30 DEG C Zirconium chloride.Feature：¹H NMR(DMSO d⁶)δppm: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 fluorenes are the zirconium metal catalyzer of ligand silicon bridge even

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

(4) the cyclohexyl chloride silane of 20mmol is dissolved in 50mL ether, is cooled to -78 DEG C, and the butyl lithium of 20mmol is added dropwise, The zirconium chloride that 1eq is added after adding is gone back after mixture is stirred overnight, 10mmol ligands is added dropwise and are dissolved in 30ml ether Mixed liquor.After being added dropwise, mixture is stirred overnight, and is then evaporated solvent and with dichloromethane extracted residues, is merged organic Phase, dried over sodium sulfate, filtering then evaporates solvent under vacuum.In order to purify, residue is dissolved in pentane, solution warp Silica gel filters and crystallization can be obtained corresponding 3,6- difluoros fluorenes -2- fluorine cyclopentadiene-cyclohexyl silicon substrate-dichloride at -30 DEG C Zirconium.Feature：¹H NMR(DMSO d⁶)δppm: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 fluorenes are the zirconium metal catalyzer of ligand silicon bridge even

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

(2) with 1 step of embodiment (2)

(4) 20mmol cyclohexyl chlorides silane is dissolved in 50mL ether, is cooled to -78 DEG C, the butyl lithium of 20mmol is added dropwise, The zirconium chloride that 1eq is added after adding is gone back after mixture is stirred overnight, 10mmol ligands is added dropwise and are dissolved in 30ml ether Mixed liquor.After being added dropwise, mixture is stirred overnight, and is then evaporated solvent and with dichloromethane extracted residues, is merged organic Phase, dried over sodium sulfate, filtering then evaporates solvent under vacuum.In order to purify, residue is dissolved in pentane, solution warp Silica gel filters and crystallization can be obtained corresponding 3- ethyls fluorenes -2- fluorine cyclopentadiene-cyclohexyl silicon substrate-dichloride at -30 DEG C Zirconium.Feature：¹H NMR(DMSO d⁶)δppm: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), 2.60 (m, 2H, CH₂),1.25(m,3H,CH₃), 0.85 (m, 10H, cyclohexyl H).

(embodiment 13) 3- fluorine substituted fluorenes are the titanium metal catalyst of ligand silicon bridge even

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

(4) the cyclohexyl chloride silane of 20mmol is dissolved in 50mL ether, is cooled to -78 DEG C, and the butyl lithium of 20mmol is added dropwise, The titanium tetrachloride that 1eq is added after adding is gone back after mixture is stirred overnight, 10mmol ligands is added dropwise and are dissolved in 30ml ether Mixed liquor.After being added dropwise, mixture is stirred overnight, and is then evaporated solvent and with dichloromethane extracted residues, is merged organic Phase, dried over sodium sulfate, filtering then evaporates solvent under vacuum.In order to purify, residue is dissolved in pentane, solution warp Silica gel filters and crystallization can be obtained corresponding 3- fluorine fluorenes -2- fluorine cyclopentadiene-cyclohexyl chloride silicon substrate-dichloride at -30 DEG C Titanium.Feature：¹H NMR(DMSO d⁶)δppm: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), 6.21 (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 fluorenes are the titanium metal catalyst of ligand silicon bridge even

(4) the 1 cyclohexyl chloride silane of 20mmol is dissolved in 50mL ether, is cooled to -78 DEG C, the butyl of 20mmol is added dropwise Lithium adds the titanium tetrachloride of 1eq after adding, go back after mixture is stirred overnight, 10mmol ligands are added dropwise and are dissolved in 30ml ether In mixed liquor.After being added dropwise, mixture is stirred overnight, and is then evaporated solvent and with dichloromethane extracted residues, is merged Organic phase, dried over sodium sulfate, filtering then evaporates solvent under vacuum.In order to purify, residue is dissolved in pentane, it is molten Liquid is filtered through silica gel and crystallization can be obtained corresponding 3,6- difluoros fluorenes -2- fluorine cyclopentadiene-cyclohexyl chloride silane-at -30 DEG C Titanium chloride.Feature：¹H NMR(DMSO d⁶)δppm: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 fluorenes are the titanium metal catalyst of ligand silicon bridge even

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

(4) the cyclohexyl chloride silane of 20mmol is dissolved in 50mL ether, is cooled to -78 DEG C, and the butyl lithium of 20mmol is added dropwise, The titanium tetrachloride that 1eq is added after adding is gone back after mixture is stirred overnight, 10mmol ligands is added dropwise and are dissolved in 30ml ether Mixed liquor.After being added dropwise, mixture is stirred overnight, and is then evaporated solvent and with dichloromethane extracted residues, is merged organic Phase, dried over sodium sulfate, filtering then evaporates solvent under vacuum.In order to purify, residue is dissolved in pentane, solution warp Silica gel filters and crystallization can be obtained corresponding 3- ethyls fluorenes -2- fluorine cyclopentadiene-cyclohexyl silicon substrate-dichloride at -30 DEG C Titanium.Feature：¹H NMR(DMSO d⁶)δppm: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), 2.60 (m, 2H, CH₂),1.25(m,3H,CH₃), 0.85 (m, 10H, cyclohexyl H).

(embodiment 16) 3- fluorine substituted fluorenes are the hafnium metallic catalyst of ligand silicon bridge even

(4) the cyclohexyl chloride silane of 20mmol is dissolved in 50mL ether, is cooled to -78 DEG C, and the butyl lithium of 20mmol is added dropwise, The hafnium tetrachloride that 1eq is added after adding is gone back after mixture is stirred overnight, 10mmol ligands is added dropwise and are dissolved in 30ml ether Mixed liquor.After being added dropwise, mixture is stirred overnight, and is then evaporated solvent and with dichloromethane extracted residues, is merged organic Phase, dried over sodium sulfate, filtering then evaporates solvent under vacuum.In order to purify, residue is dissolved in pentane, solution warp Silica gel filters and crystallization can be obtained corresponding 3- fluorine fluorenes -2- fluorine cyclopentadiene-cyclohexyl silicon substrate-hafnium dichloride at -30 DEG C. Feature：¹H NMR(DMSO d⁶)δppm:7.87 (m, 1H, aromatic ring H) 7.55 (m, 3 H, 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 fluorenes are the hafnium metallic catalyst of ligand silicon bridge even

(4) the cyclohexyl chloride silane of 20mmol is dissolved in 50mL ether, is cooled to -78 DEG C, and the butyl lithium of 20mmol is added dropwise, The hafnium tetrachloride that 1eq is added after adding is gone back after mixture is stirred overnight, 10mmol ligands is added dropwise and are dissolved in 30ml ether Mixed liquor.After being added dropwise, mixture is stirred overnight, and is then evaporated solvent and with dichloromethane extracted residues, is merged organic Phase, dried over sodium sulfate, filtering then evaporates solvent under vacuum.In order to purify, residue is dissolved in pentane, solution warp Silica gel filters and crystallization can be obtained corresponding 3,6- difluoros fluorenes -2- fluorine cyclopentadiene-cyclohexyl silicon substrate-dichloride at -30 DEG C Hafnium.Feature：¹H NMR(DMSO d⁶)δppm: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 fluorenes are the hafnium metallic catalyst of ligand silicon bridge even

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

(4) the cyclohexyl chloride silane of 20mmol is dissolved in 50mL ether, is cooled to -78 DEG C, and the butyl lithium of 20mmol is added dropwise, The hafnium tetrachloride that 1eq is added after adding is gone back after mixture is stirred overnight, 10mmol ligands is added dropwise and are dissolved in 30ml ether Mixed liquor.After being added dropwise, mixture is stirred overnight, and is then evaporated solvent and with dichloromethane extracted residues, is merged organic Phase, dried over sodium sulfate, filtering then evaporates solvent under vacuum.In order to purify, residue is dissolved in pentane, solution warp Silica gel filters and crystallization can be obtained corresponding 3- ethyls fluorenes -2- fluorine cyclopentadiene-cyclohexyl silicon substrate-dichloride at -30 DEG C Hafnium.Feature：¹H NMR(DMSO d⁶)δppm: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- indenos [1,2-b] pyridyl group is the zirconium metal catalyzer of ligand carbon bridging

(1) synthesis of 2- fluorine cyclopentadienyl group：10mmol sodium bits are added in 10ml ethyl alcohol.Then the first of 10mmol is added Benzophenone.Then 20mmol 2- fluorine cyclopentadiene is added dropwise, mixture stirs 15 hours under reflux.Obtained product is then with water It dilutes and with extraction into heptane, evaporates organic phase, after excessive 2- fluorine cyclopentadienyl group is removed in distillation, after being extracted with ethyl acetate, Dry, filtering is evaporated.

(2) 10mmol 5H- indenos [1,2-b] pyridinium dissolution in 50ml ether and with the 1.6M of 10mmol n-BuLis Hexane solution mixes, and then stirs a few houres.Equimolar substitution 2- fluorine cyclopentadiene is added, and mixture is stirred overnight. Then with 50ml water hydrolysis reaction mixtures, organic phase is dried with sodium sulphate and evaporates solvent under vacuum, it is spare.

(3) the 1 of 20mmol, 3,5- trifluoro-benzenes are dissolved in 50mL ether, are cooled to -78 DEG C, and the butyl lithium of 20mmol is added dropwise, The zirconium chloride that 1eq is added after adding is gone back after mixture is stirred overnight, 10mmol ligands is added dropwise and are dissolved in 30ml ether Mixed liquor.After being added dropwise, mixture is stirred overnight, and is then evaporated solvent and with dichloromethane extracted residues, is merged organic Phase, dried over sodium sulfate, filtering then evaporates solvent under vacuum.In order to purify, residue is dissolved in pentane, solution warp Silica gel filters and crystallization can be obtained corresponding 5H- indenos [1,2-b] pyridine -2- fluorine cyclopentadiene-two -1,3,5- at -30 DEG C Trifluorophenyl-zirconium dichloride.Feature：¹H NMR(DMSO d⁶)δppm: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- indenos [1,2-b] pyridyl group is the titanium metal catalyst of ligand carbon bridging

(1) synthesis of 2- fluorine cyclopentadienyl group, with 19 step of embodiment (1).

(2) 10mmol 5H- indenos [1,2-b] pyridinium dissolution in 50ml ether and with the 1.6M of 10mmol n-BuLis Hexane solution mixes, and then stirs a few houres.It adds equimolar 2- fluorine cyclopentadienyl group (being same as above) and mixture is stirred Night.Then with 50ml water hydrolysis reaction mixtures, organic phase is dried with sodium sulphate and evaporates solvent under vacuum, it is spare.

(3) the 1 of 20mmol, 3,5- trifluoro-benzenes are dissolved in 50mL ether, are cooled to -78 DEG C, and the butyl lithium of 20mmol is added dropwise, The titanium tetrachloride that 1eq is added after adding is gone back after mixture is stirred overnight, 10mmol ligands is added dropwise and are dissolved in 30ml ether Mixed liquor.After being added dropwise, mixture is stirred overnight, and is then evaporated solvent and with dichloromethane extracted residues, is merged organic Phase, dried over sodium sulfate, filtering then evaporates solvent under vacuum.In order to purify, residue is dissolved in pentane, solution warp Silica gel filters and crystallization can be obtained corresponding 5H- indenos [1,2-b] pyridine -2- fluorine cyclopentadiene-two -1,3,5- at -30 DEG C Trifluorophenyl-titanium chloride.Feature：¹H NMR(DMSO d⁶)δppm: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- indenos [1,2-b] pyridyl group is the hafnium metallic catalyst of ligand carbon bridging

(3) the 1 of 20mmol, 3,5- trifluoro-benzenes are dissolved in 50mL ether, are cooled to -78 DEG C, and the butyl lithium of 20mmol is added dropwise, The hafnium tetrachloride that 1eq is added after adding is gone back after mixture is stirred overnight, 10mmol ligands is added dropwise and are dissolved in 30ml ether Mixed liquor.After being added dropwise, mixture is stirred overnight, and is then evaporated solvent and with dichloromethane extracted residues, is merged organic Phase, dried over sodium sulfate, filtering then evaporates solvent under vacuum.In order to purify, residue is dissolved in pentane, solution warp Silica gel filters and crystallization can be obtained corresponding 5H- indenos [1,2-b] pyridine -2- fluorine cyclopentadiene-two -1,3,5- at -30 DEG C Trifluorophenyl-hafnium dichloride.Feature：¹H NMR(DMSO d⁶) 8.50 (m, 1 H, 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, 1 H, 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- indenos [1,2-b] pyridyl group is the zirconium metal catalyzer of ligand silicon bridge even

(1) synthesis of 2- fluorine cyclopentadienyl group：With 19 step of embodiment (1).

(2) 1.6M hexane solution of 5H- indenos [1,2-b] pyridinium dissolution in 50ml ether and with 10mmol n-BuLis Mixing, then stirs a few houres.Equimolar substitution 2- fluorine cyclopentadiene is added, and mixture is stirred overnight.Then with 50ml water hydrolysis reaction mixtures dry organic phase with sodium sulphate and evaporate solvent under vacuum, spare.

(3) the cyclohexyl chloride silane of 20mmol is dissolved in 50mL ether, is cooled to -78 DEG C, and the butyl lithium of 20mmol is added dropwise, The zirconium chloride that 1eq is added after adding is gone back after mixture is stirred overnight, 10mmol ligands is added dropwise and are dissolved in 30ml ether Mixed liquor.After being added dropwise, mixture is stirred overnight, and is then evaporated solvent and with dichloromethane extracted residues, is merged organic Phase, dried over sodium sulfate, filtering then evaporates solvent under vacuum.In order to purify, residue is dissolved in pentane, solution warp Silica gel filters and crystallization can be obtained corresponding 5H- indenos [1,2-b] pyridine -2- fluorine cyclopentadiene-cyclohexyl silicon at -30 DEG C Base-zirconium dichloride.Feature：¹H NMR(DMSO d⁶)δppm: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, 1 H, aromatic ring H), 6.21 (m, 1H, rings penta Diene 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- indenos [1,2-b] pyridyl group is the titanium metal catalyst of ligand silicon bridge even

(3) the cyclohexyl chloride silane of 20mmol is dissolved in 50mL ether, is cooled to -78 DEG C, and the butyl lithium of 20mmol is added dropwise, The titanium tetrachloride that 1eq is added after adding is gone back after mixture is stirred overnight, 10mmol ligands is added dropwise and are dissolved in 30ml ether Mixed liquor.After being added dropwise, mixture is stirred overnight, and is then evaporated solvent and with dichloromethane extracted residues, is merged organic Phase, dried over sodium sulfate, filtering then evaporates solvent under vacuum.In order to purify, residue is dissolved in pentane, solution warp Silica gel filters and crystallization can be obtained corresponding 5H- indenos [1,2-b] pyridine -2- fluorine cyclopentadiene-cyclohexyl silicon at -30 DEG C Base-titanium chloride.Feature：¹H NMR(DMSO d⁶)δppm: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, 1 H, aromatic ring H), 6.21 (m, 1H, rings penta Diene 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- indenos [1,2-b] pyridyl group is the hafnium metallic catalyst of ligand silicon bridge even

(3) the cyclohexyl chloride silane of 20mmol is dissolved in 50mL ether, is cooled to -78 DEG C, and the butyl lithium of 20mmol is added dropwise, The hafnium tetrachloride that 1eq is added after adding is gone back after mixture is stirred overnight, 10mmol ligands is added dropwise and are dissolved in 30ml ether Mixed liquor.After being added dropwise, mixture is stirred overnight, and is then evaporated solvent and with dichloromethane extracted residues, is merged organic Phase, dried over sodium sulfate, filtering then evaporates solvent under vacuum.In order to purify, residue is dissolved in pentane, solution warp Silica gel filters and crystallization can be obtained corresponding 5H- indenos [1,2-b] pyridine -2- fluorine cyclopentadiene-cyclohexyl silicon at -30 DEG C Base-hafnium dichloride.Feature：¹H NMR(DMSO d⁶)δppm: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, 1 H, aromatic ring H), 6.21 (m, 1H, rings penta Diene 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- indenos [1,2-b] thiopyranyl is the zirconium metal catalyzer of ligand carbon bridging

(1) synthesis of 2- fluorine cyclopentadienyl group：With 19 step of example (1)

(2) 10mmol 5H- indenos [1,2-b] thio-pyrylium be dissolved in 50ml ether and with 10mmol n-BuLis 1.6M hexane solutions mix, and then stir a few houres.Equimolar substitution 2- fluorine cyclopentadiene is added, and mixture is stirred Night.Then with 50ml water hydrolysis reaction mixtures, organic phase is dried with sodium sulphate and evaporates solvent under vacuum, it is spare.

(3) the 1 of 20mmol, 3,5- trifluoro-benzenes are dissolved in 50mL ether, are cooled to -78 DEG C, and the butyl lithium of 20mmol is added dropwise, The zirconium chloride that 1eq is added after adding is gone back after mixture is stirred overnight, 10mmol ligands is added dropwise and are dissolved in 30ml ether Mixed liquor.After being added dropwise, mixture is stirred overnight, and is then evaporated solvent and with dichloromethane extracted residues, is merged organic Phase, dried over sodium sulfate, filtering then evaporates solvent under vacuum.In order to purify, residue is dissolved in pentane, solution warp Silica gel filters and crystallization can be obtained corresponding 5H- indenos [1,2-b] thio-pyrylium -2- fluorine cyclopentadiene-two -1 at -30 DEG C, 3,5- trifluorophenyls-zirconium dichloride.Feature：¹H NMR(DMSO d⁶)δppm:8.90 (m, 1H, aromatic ring H), 8.35 (m, 1H, virtues 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, rings penta 2 Alkene H), 2.65 (m, 2H, aromatic ring H).

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

(2) 10mmol 5H- indenos [1,2-b] thio-pyrylium be dissolved in 50ml ether and with 10mmol n-BuLis 1.6M hexane solutions mix, and then stir a few houres.It adds equimolar 2- fluorine cyclopentadienyl group (being same as above) and mixture stirs It mixes overnight.Then with 50ml water hydrolysis reaction mixtures, organic phase is dried with sodium sulphate and evaporates solvent under vacuum, it is spare.

(3) the 1 of 20mmol, 3,5- trifluoro-benzenes are dissolved in 50mL ether, are cooled to -78 DEG C, and the butyl lithium of 20mmol is added dropwise, The titanium tetrachloride that 1eq is added after adding is gone back after mixture is stirred overnight, 10mmol ligands is added dropwise and are dissolved in 30ml ether Mixed liquor.After being added dropwise, mixture is stirred overnight, and is then evaporated solvent and with dichloromethane extracted residues, is merged organic Phase, dried over sodium sulfate, filtering then evaporates solvent under vacuum.In order to purify, residue is dissolved in pentane, solution warp Silica gel filters and crystallization can be obtained corresponding 5H- indenos [1,2-b] thio-pyrylium -2- fluorine cyclopentadiene-two -1 at -30 DEG C, 3,5- trifluorophenyls-titanium chloride.Feature：¹H NMR(DMSO d⁶)δppm:8.90 (m, 1H, aromatic ring H), 8.35 (m, 1H, virtues 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, rings penta 2 Alkene H), 2.65 (m, 2H, aromatic ring H).

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

(3) the 1 of 20mmol, 3,5- trifluoro-benzenes are dissolved in 50mL ether, are cooled to -78 DEG C, and the butyl lithium of 20mmol is added dropwise, The hafnium tetrachloride that 1eq is added after adding is gone back after mixture is stirred overnight, 10mmol ligands is added dropwise and are dissolved in 30ml ether Mixed liquor.After being added dropwise, mixture is stirred overnight, and is then evaporated solvent and with dichloromethane extracted residues, is merged organic Phase, dried over sodium sulfate, filtering then evaporates solvent under vacuum.In order to purify, residue is dissolved in pentane, solution warp Silica gel filters and crystallization can be obtained corresponding 5H- indenos [1,2-b] thio-pyrylium pyridine -2- fluorine cyclopentadiene-two-at -30 DEG C 1,3,5- trifluorophenyl-hafnium dichloride.Feature：¹H NMR(DMSO d⁶) 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 28) 5H- indenos [1,2-b] thiopyranyl is the zirconium metal catalyzer of ligand silicon bridge even

(2) 5H- indenos [1,2-b] thio-pyrylium is dissolved in the 1.6M hexanes in 50ml ether and with 10mmol n-BuLis Solution mixes, and then stirs a few houres.Equimolar substitution 2- fluorine cyclopentadiene is added, and mixture is stirred overnight.Then With 50ml water hydrolysis reaction mixtures, organic phase is dried with sodium sulphate and evaporates solvent under vacuum, it is spare.

(3) the cyclohexyl chloride silane of 20mmol is dissolved in 50mL ether, is cooled to -78 DEG C, and the butyl lithium of 20mmol is added dropwise, The zirconium chloride that 1eq is added after adding is gone back after mixture is stirred overnight, 10mmol ligands is added dropwise and are dissolved in 30ml ether Mixed liquor.After being added dropwise, mixture is stirred overnight, and is then evaporated solvent and with dichloromethane extracted residues, is merged organic Phase, dried over sodium sulfate, filtering then evaporates solvent under vacuum.In order to purify, residue is dissolved in pentane, solution warp Silica gel filters and crystallization can be obtained corresponding 5H- indenos [1,2-b] thio-pyrylium -2- fluorine cyclopentadiene-hexamethylene at -30 DEG C Base silicon substrate-zirconium dichloride.Feature：¹H NMR(DMSO d⁶)δppm: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, 1 H, 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).

(embodiment 29) 5H- indenos [1,2-b] thiopyranyl is the titanium metal catalyst of ligand silicon bridge even

(3) the cyclohexyl chloride silane of 20mmol is dissolved in 50mL ether, is cooled to -78 DEG C, and the butyl lithium of 20mmol is added dropwise, The titanium tetrachloride that 1eq is added after adding is gone back after mixture is stirred overnight, 10mmol ligands is added dropwise and are dissolved in 30ml ether Mixed liquor.After being added dropwise, mixture is stirred overnight, and is then evaporated solvent and with dichloromethane extracted residues, is merged organic Phase, dried over sodium sulfate, filtering then evaporates solvent under vacuum.In order to purify, residue is dissolved in pentane, solution warp Silica gel filters and crystallization can be obtained corresponding 5H- indenos [1,2-b] thio-pyrylium -2- fluorine cyclopentadiene-hexamethylene at -30 DEG C Base silicon substrate-titanium chloride.Feature：¹H NMR(DMSO d⁶)δppm: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, 1 H, 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).

(embodiment 30) 5H- indenos [1,2-b] thiopyranyl is the hafnium metallic catalyst of ligand silicon bridge even

(3) the cyclohexyl chloride silane of 20mmol is dissolved in 50mL ether, is cooled to -78 DEG C, and the butyl lithium of 20mmol is added dropwise, The hafnium tetrachloride that 1eq is added after adding is gone back after mixture is stirred overnight, 10mmol ligands is added dropwise and are dissolved in 30ml ether Mixed liquor.After being added dropwise, mixture is stirred overnight, and is then evaporated solvent and with dichloromethane extracted residues, is merged organic Phase, dried over sodium sulfate, filtering then evaporates solvent under vacuum.In order to purify, residue is dissolved in pentane, solution warp Silica gel filters and crystallization can be obtained corresponding 5H- indenos [1,2-b] thio-pyrylium -2- fluorine cyclopentadiene-hexamethylene at -30 DEG C Base silicon substrate-hafnium dichloride.Feature：¹H NMR(DMSO d⁶)δppm: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, 1 H, 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 carried out further in detail the purpose of the present invention, technical solution and advantageous effect It describes in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in the guarantor of the present invention Within the scope of shield.

Catalyst activity test experiments：

Primary raw material and its pretreatment:

The operation for relating to metal-organic preparation and processing is all made of standard glove box and Schlenk skills Art carries out under high pure nitrogen.Solvent toluene, analysis is pure, using preceding above for 24 hours straight with metallic sodium and benzophenone continuous backflow Distillation sealing is spare after to discoloration.1- decene for polymerisation carries out pure purchased from Aldrich and by water and oxygen scavenger Change.The evacuated deoxygenation dehumidifying of polymerization experiment reaction bulb, is replaced at least 3~4 times with high pure nitrogen, is cooled down under nitrogen protection. Prepare the toluene solution of certain density major catalyst and co-catalyst.When oil bath temperature reaches set temperature, using drying Glass syringe a certain amount of co-catalyst is added in glass reaction bottle, 1- decene is sequentially added under stirring, toluene, is advocated peace The toluene solution of cocatalyst keeps oil bath temperature, starts to polymerize.Reaction after a certain period of time, is terminated with alcohol hydrochloric acid solution Reaction, is then filtered separation by polymerizate.After deionized water flushing several times is added in upper layer product, carry out at liquid separation Reason, takes supernatant liquor that unreacted monomer and solvent is distilled off through normal pressure, is then obtained in 90~160 DEG C of section vacuum distillations Target product.

The concentration of catalytic component is as follows：Metallocene catalyst：1% toluene solution；Main co-catalyst:0.1%Ph₃C⁺B (C₆F₅)₄Toluene solution；Cocatalyst:25%Al (iBu)₃Toluene solution.

Three kinds of catalytic components：The molar ratio of metallocene catalyst/main co-catalyst/cocatalyst is 1:2:6.

Experimental method:

By dry 50ml toluene and 1- decene (370g, 2.64mol) be added to 1 500ml with magnetic agitation In reaction bulb.When 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 co-catalyst [CPh₃]⁺[B(C₆F₅)₄]^-(0.18g, 0.020mmol) and cocatalyst (iBu)₃The toluene of Al (0.10g, 0.50mmol) is molten Liquid, which is injected into reaction bulb, makes it start to react, and heating makes reaction temperature rise to 70 DEG C, maintains isothermal reaction 1 hour.Then 5ml alcohol hydrochloric acid solution is added and terminates reaction.After removing unreacted 1- decene and solvent toluene under vacuum, remaining production is weighed The weight of object calculates catalytic activity and 1- decene conversion ratios.

Example 1：Metallocene catalyst：- two -1,3,5- trifluorophenyls of 5H- indenos [1,2-b] pyridine -2- fluorine cyclopentadiene - Zirconium dichloride

Example 2：Metallocene catalyst：- two -1,3,5- trifluorophenyls of 5H- indenos [1,2-b] pyridine -2- fluorine cyclopentadiene - Titanium chloride

Example 3：Metallocene catalyst：- two -1,3,5- trifluorophenyls of 5H- indenos [1,2-b] pyridine -2- fluorine cyclopentadiene - Hafnium dichloride

Example 4：Metallocene catalyst：5H- indenos [1,2-b] pyridine -2- fluorine cyclopentadiene-cyclohexyl silicon substrate-dichloride Zirconium

Example 5：Metallocene catalyst：5H- indenos [1,2-b] pyridine -2- fluorine cyclopentadiene-cyclohexyl silicon substrate-dichloride Titanium

Example 6：Metallocene catalyst：- two -1,3,5- trifluoros of 5H- indenos [1,2-b] thio-pyrylium -2- fluorine cyclopentadiene Phenyl-zirconium dichloride

Example 7：Metallocene catalyst：- two -1,3,5- trifluoros of 5H- indenos [1,2-b] thio-pyrylium -2- fluorine cyclopentadiene Phenyl-titanium chloride

Example 8：Metallocene catalyst：- two -1,3,5- three of 5H- indenos [1,2-b] thio-pyrylium pyridine -2- fluorine cyclopentadiene Fluorophenyl-hafnium dichloride

Example 9：Metallocene catalyst：5H- indenos [1,2-b] thio-pyrylium -2- fluorine cyclopentadiene-cyclohexyl silicon substrate-two Zirconium chloride

Example 10：Metallocene catalyst：5H- indenos [1,2-b] thio-pyrylium -2- fluorine cyclopentadiene-cyclohexyl silicon substrate-two Titanium chloride

Experimental result conclusive table 1

Experimental result conclusive table 2

To sum up, metallocene poly-alpha olefins catalyst of the present invention, stable structure, high catalytic efficiency, preparation method of the invention It is easy to operate, yield is high, raw material is easy to get, at low cost, environmental pollution is small, be easy to industrialized production.

Claims

1. a kind of synthetic lubricant base oil metallocene poly-alpha olefins catalyst, it is characterised in that：The catalyst structure packet Include substituted aromatic base, bridge formation atom, unsubstituted or 3 is monosubstituted or 5H- indenos [1,2-b] pyridyl groups of bis- substitutions of 3,6- or It is unsubstituted or 3 is monosubstituted or 3,5H- indenos [1,2-b] thiopyranyl of bis- substitutions of 6-, metal dentate, structural formula For：

Wherein：

Substituted aromatic base Ar is

X is N or S；

Y is bridge formation atom, is silicon or carbon；

R₁It is the substituent group on cyclopentadiene, is fluorine atom or hydrogen atom；R₂Substituent group on benzothiophene, be fluorine atom or Person's hydrogen atom；R₃It is substituent group on indoles, is fluorine atom or hydrogen atom；

R₄It is the substituent group on bridge formation atom, is cyclohexyl, cyclopenta or cyclobutyl when bridge formation atom is silicon；Work as bridge formation atom For carbon when, for 1,3,5- tri- substitution or monosubstituted disubstituted phenyl；

R₅It is described 3 monosubstituted or bis- substitutions of 3,6- 5H- indenos [1,2-b] pyridyl groups or 3 monosubstituted or bis- substitutions of 3,6- 5H- indenos [1,2-b] thiopyranyl on substituent group, be the alkane of all straight chains of halogen or carbon atom number 2~24, branch Base；

M is metal zirconium or hafnium or titanium；L is the halogen being coordinated with metal.

2. catalyst according to claim 1, wherein：

1) 5H- indenos [1,2-b] pyridyl group is one of the group in following groups：5H- indenos [1,2-b] pyridyl group, 3- Fluorine 5H- indenos [1,2-b] pyridyl group, 3,6- difluoro 5H- indenos [1,2-b] pyridyl group, 3- bromine 5H- indenos [1,2-b] pyridyl group, 3,6- dibromo 5H- indenos [1,2-b] pyridyl groups, 3- iodine 5H- indenos [1,2-b] pyridyl group, 3,6- diiodo- 5H- indenos [1,2-b] Pyridyl group, 3- ethyl 5H- indenos [1,2-b] pyridyl group, 3,6- diethyl 5H- indenos [1,2-b] pyridyl group, 3- propyl 5H- indenes And [1,2-b] pyridyl group, 3,6- dipropyl 5H- indenos [1,2-b] pyridyl group, 3- butyl 5H- indenos [1,2-b] pyridyl group, 3, 6- dibutyl 5H- indenos [1,2-b] pyridyl group, 3- isopropyl 5H- indenos [1,2-b] pyridyl group, 3,6- diisopropyl 5H- indenos [1,2-b] pyridyl group, 3- isobutyl group 5H- indenos [1,2-b] pyridyl group, 3,6- diisobutyl 5H- indenos [1,2-b] pyridyl group, 3- amyl 5H- indenos [1,2-b] pyridyl group, 3,6- diamyl 5H- indenos [1,2-b] pyridyl group, 3- isopentyl 5H- indenos [1, 2-b] pyridyl group, 3,6- diisoamyl 5H- indenos [1,2-b] pyridyl group, 3- tertiary butyl 5H- indenos [1,2-b] pyridyl group, 3,6- Di-t-butyl 5H- indenos [1,2-b] pyridyl group, 3- allyl 5H- indenos [1,2-b] pyridyl group, 3,6- diallyl 5H- indenos [1,2-b] pyridyl group, 3- hexyl 5H- indenos [1,2-b] pyridyl group, 3,6- dihexyl 5H- indenos [1,2-b] pyridyl group, 3- are different Hexyl 5H- indenos [1,2-b] pyridyl group, 3,6- bis- isohesyl 5H- indenos [1,2-b] pyridyl group, 3- t-butylethyl 5H- indenos [1,2-b] pyridyl group, 3,6- di-t-butyls ethyl 5H- indenos [1,2-b] pyridyl group, 3- heptyl 5H- indenos [1,2-b] pyridine Base, 3,6- diheptyl 5H- indenos [1,2-b] pyridyl group, different heptyl 5H- indenos [1, the 2-b] pyridyl groups of 3-, 3,6-, bis- different heptyl 5H- indenos [1,2-b] pyridyl group, 3- tertiary butyls propyl 5H- indenos [1,2-b] pyridyl group, 3,6- di-t-butyl propyl 5H- indenos [1,2-b] pyridyl group, 3- octyl 5H- indenos [1,2-b] pyridyl group, 3,6- dioctyl 5H- indenos [1,2-b] pyridyl group, 3- are different Octyl 5H- indenos [1,2-b] pyridyl group, 3,6- diisooctyl 5H- indenos [1,2-b] pyridyl group, 3- tertiary butyl butyl 5H- indenos [1,2-b] pyridyl group, 3,6- di-t-butyls butyl 5H- indenos [1,2-b] pyridyl group, 3- undecyl 5H- indenos [1,2-b] pyrrole Piperidinyl, 3,6- bis--undecyl 5H- indenos [1,2-b] pyridyl group, 3- dodecyl 5H- indenos [1,2-b] pyridyl group, 3,6- Two-dodecyl 5H- indenos [1,2-b] pyridyl groups, 3- tridecyl 5H- indenos [1,2-b] pyridyl group, 3,6-, bis--tridecanes Base 5H- indenos [1,2-b] pyridyl group, 3- myristyl 5H- indenos [1,2-b] pyridyl group, 3,6-, bis--myristyl 5H- indenos [1,2-b] pyridyl group, 3- pentadecyl 5H- indenos [1,2-b] pyridyl group, 3,6- bis--pentadecyl 5H- indenos [1,2-b] pyrrole Piperidinyl, 3- cetyl 5H- indenos [1,2-b] pyridyl group, 3,6- bis--cetyl 5H- indenos [1,2-b] pyridyl group, 3- ten Seven alkyl 5H- indenos [1,2-b] pyridyl groups, 3,6- bis--heptadecyl 5H- indenos [1,2-b] pyridyl group, 3- octadecyls 5H- Indeno [1,2-b] pyridyl group, 3,6- bis--octadecyl 5H- indenos [1,2-b] pyridyl group, 3- nonadecyl 5H- indenos [1,2- B] pyridyl group, 3,6- bis--nonadecyl 5H- indenos [1,2-b] pyridyl group, 3- eicosyl 5H- indenos [1,2-b] pyridyl group, 3,6- bis--eicosyl 5H- indenos [1,2-b] pyridyl groups, 3- heneicosyl 5H- indenos [1,2-b] pyridyl group, 3,6- bis-- Heneicosyl 5H- indenos [1,2-b] pyridyl group, 3- docosyl 5H- indenos [1,2-b] pyridyl group, 3,6- bis--two 12 Alkyl 5H- indenos [1,2-b] pyridyl group, 3- tricosyl 5H- indenos [1,2-b] pyridyl group, 3,6-, bis--tricosyls 5H- indenos [1,2-b] pyridyl group, 3- tetracosyl 5H- indenos [1,2-b] pyridyl group, 3,6-, bis--tetracosyl 5H- indenes And [1,2-b] pyridyl group；

2) 5H- indenos [1,2-b] thiopyranyl is one of the group in following groups:5H- indenos [1,2-b] thio pyrrole It mutters base, 3- fluorine 5H- indenos [1,2-b] thiopyranyl, 3,6- difluoro 5H- indenos [1,2-b] thiopyranyl, 3- bromine 5H- indenes And [1,2-b] thiopyranyl, 3,6- dibromo 5H- indenos [1,2-b] thiopyranyl, 3- iodine 5H- indenos [1,2-b] thio pyrrole It mutters base, 3,6- diiodo- 5H- indenos [1,2-b] thiopyranyl, 3- ethyl 5H- indenos [1,2-b] thiopyranyl, 3,6- diethyls Base 5H- indenos [1,2-b] thiopyranyl, 3- propyl 5H- indenos [1,2-b] thiopyranyl, 3,6- dipropyl 5H- indenos [1,2-b] thiopyranyl, 3- butyl 5H- indenos [1,2-b] thiopyranyl, 3,6- dibutyl 5H- indenos [1,2-b] are thio Pyranose, 3- isopropyl 5H- indenos [1,2-b] thiopyranyl, 3,6- diisopropyl 5H- indenos [1,2-b] thiopyranyl, 3- isobutyl group 5H- indenos [1,2-b] thiopyranyl, 3,6- diisobutyl 5H- indenos [1,2-b] thiopyranyl, 3- amyls 5H- indenos [1,2-b] thiopyranyl, 3,6- diamyl 5H- indenos [1,2-b] thiopyranyl, 3- isopentyl 5H- indenos [1,2-b] thiopyranyl, 3,6- diisoamyl 5H- indenos [1,2-b] thiopyranyl, 3- tertiary butyl 5H- indenos [1,2-b] Thiopyranyl, 3,6- di-t-butyl 5H- indenos [1,2-b] thiopyranyl, 3- allyl 5H- indenos [1,2-b] thio pyrrole It mutters base, 3,6- diallyl 5H- indenos [1,2-b] thiopyranyl, 3- hexyl 5H- indenos [1,2-b] thiopyranyl, 3,6- Dihexyl 5H- indenos [1,2-b] thiopyranyl, 3- isohesyl 5H- indenos [1,2-b] thiopyranyl, 3,6-, bis- isohesyls 5H- indenos [1,2-b] thiopyranyl, 3- t-butylethyl 5H- indenos [1,2-b] thiopyranyl, 3,6- di-t-butyl second Base 5H- indenos [1,2-b] thiopyranyl, 3- heptyl 5H- indenos [1,2-b] thiopyranyl, 3,6- diheptyl 5H- indenos Different heptyl 5H- indenos [1, the 2-b] thiopyranyl of [1,2-b] thiopyranyl, 3-, 3,6-, bis- different heptyl 5H- indenos [1,2-b] Thiopyranyl, 3- tertiary butyls propyl 5H- indenos [1,2-b] thiopyranyl, 3,6- di-t-butyl propyl 5H- indenos [1,2- B] thiopyranyl, 3- octyl 5H- indenos [1,2-b] thiopyranyl, 3,6- dioctyl 5H- indenos [1,2-b] thio-pyrylium Base, 3- iso-octyl 5H- indenos [1,2-b] thiopyranyl, 3,6- diisooctyl 5H- indenos [1,2-b] thiopyranyl, uncle 3- Butyl 5H- indenos [1,2-b] thiopyranyl, 3,6- di-t-butyls butyl 5H- indenos [1,2-b] thiopyranyl, 3- Undecyl 5H- indenos [1,2-b] thiopyranyl, 3,6- bis--undecyl 5H- indenos [1,2-b] thiopyranyl, 3- ten Dialkyl group 5H- indenos [1,2-b] thiopyranyl, 3,6- bis--dodecyl 5H- indenos [1,2-b] thiopyranyl, 3- 13 Alkyl 5H- indenos [1,2-b] thiopyranyl, 3,6- bis--tridecyl 5H- indenos [1,2-b] thiopyranyl, the 3- tetradecanes Base 5H- indenos [1,2-b] thiopyranyl, 3,6- bis--myristyl 5H- indenos [1,2-b] thiopyranyl, 3- pentadecyls 5H- indenos [1,2-b] thiopyranyl, 3,6- bis--pentadecyl 5H- indenos [1,2-b] thiopyranyl, 3- cetyls 5H- indenos [1,2-b] thiopyranyl, 3,6- bis--cetyl 5H- indenos [1,2-b] thiopyranyl, 3- heptadecyls 5H- indenos [1,2-b] thiopyranyl, 3,6- bis--heptadecyl 5H- indenos [1,2-b] thiopyranyl, 3- octadecyls 5H- indenos [1,2-b] thiopyranyl, 3,6- bis--octadecyl 5H- indenos [1,2-b] thiopyranyl, 3- nonadecyls 5H- indenos [1,2-b] thiopyranyl, 3,6- bis--nonadecyl 5H- indenos [1,2-b] thiopyranyl, 3- eicosyls 5H- indenos [1,2-b] thiopyranyl, 3,6- bis--eicosyl 5H- indenos [1,2-b] thiopyranyl, 3- heneicosyls 5H- indenos [1,2-b] thiopyranyl, 3,6- bis--heneicosyl 5H- indenos [1,2-b] thiopyranyl, 3- docosane Base 5H- indenos [1,2-b] thiopyranyl, 3,6- bis--docosyl 5H- indenos [1,2-b] thiopyranyl, 3- 23 Alkyl 5H- indenos [1,2-b] thiopyranyl, 3,6- bis--tricosyl 5H- indenos [1,2-b] thiopyranyl, 3- 20 Tetraalkyl 5H- indenos [1,2-b] thiopyranyl, 3,6- bis--tetracosyl 5H- indenos [1,2-b] thiopyranyl.

3. catalyst according to claim 2 comprising 5H- indenos [1,2-b] pyridyl group, the catalyst are：

- two -1,3,5- trifluorophenyls of 5H- indenos [1,2-b] pyridine -2- fluorine cyclopentadiene-zirconium dichloride；

- two -1,3,5- trifluorophenyls of 5H- indenos [1,2-b] pyridine -2- fluorine cyclopentadiene-titanium chloride；

- two -1,3,5- trifluorophenyls of 5H- indenos [1,2-b] pyridine -2- fluorine cyclopentadiene-hafnium dichloride；

5H- indenos [1,2-b] pyridine -2- fluorine cyclopentadiene-cyclohexyl silicon substrate-zirconium dichloride；

5H- indenos [1,2-b] pyridine -2- fluorine cyclopentadiene-cyclohexyl silicon substrate-titanium chloride；Or

5H- indenos [1,2-b] pyridine -2- fluorine cyclopentadiene-cyclohexyl silicon substrate-hafnium dichloride.

4. catalyst according to claim 2 comprising 5H- indenos [1,2-b] thiopyranyl, the catalyst are：

- two -1,3,5- trifluorophenyls of 5H- indenos [1,2-b] thio-pyrylium -2- fluorine cyclopentadiene-zirconium dichloride；

- two -1,3,5- trifluorophenyls of 5H- indenos [1,2-b] thio-pyrylium -2- fluorine cyclopentadiene-titanium chloride；

- two -1,3,5- trifluorophenyls of 5H- indenos [1,2-b] thio-pyrylium pyridine -2- fluorine cyclopentadiene-hafnium dichloride；

5H- indenos [1,2-b] thio-pyrylium -2- fluorine cyclopentadiene-cyclohexyl silicon substrate-zirconium dichloride；

5H- indenos [1,2-b] thio-pyrylium -2- fluorine cyclopentadiene-cyclohexyl silicon substrate-titanium chloride；Or

5H- indenos [1,2-b] thio-pyrylium -2- fluorine cyclopentadiene-cyclohexyl silicon substrate-hafnium dichloride.

5. a kind of synthetic lubricant base oil metallocene poly-alpha olefins catalyst according to any one of claims 1-4 is answered With, it is characterised in that：Its catalyst as synthetic lubricant base oil reaction, its addition is reaction-ure mixture when reaction 0.1-10ppm wt%.