CN103509060B

CN103509060B - Metallocene compound, the carbon monoxide-olefin polymeric comprising metallocene compound and the olefine polymerizing process of use metallocene compound

Info

Publication number: CN103509060B
Application number: CN201210218662.7A
Authority: CN
Inventors: 洪思雯; 磪惠善; 孙炳吉
Original assignee: Daelim Industrial Co Ltd
Current assignee: DL Chemical Co Ltd
Priority date: 2012-06-27
Filing date: 2012-06-27
Publication date: 2016-08-10
Anticipated expiration: 2032-06-27
Also published as: CN103509060A

Abstract

Disclosing metallocene compound and include the carbon monoxide-olefin polymeric of described metallocene compound and use the olefine polymerizing process of described metallocene compound, wherein said metallocene compound can come Polymerization Alkene polymerization thing or copolymer with high polymerization activity.Following general formula metallocene compound, and (4HInd) (Cp ') MX₂nullWherein，4HInd is the group with tetrahydro indenyl core，Cp ' is the group with cyclopentadienyl group core，And 4HInd and Cp ' is unsubstituted or is substituted with one or more substituents，And described substituent group is same to each other or different to each other，Described substituent group is the alkyl selected from 1 to 20 carbon atom、Alkoxyl、AIkylsilyl groups、Alkyl siloxy、Alkyl amino or haloalkyl，The cycloalkyl of 3 to 20 carbon atoms，The aryl of 6 to 20 carbon atoms、Aryl alkyl、Arylsilyl groups、Alkylaryl or aryloxy group，The dialkyl amido of 2 to 20 carbon atoms，Halogen atom and the group of amino，And M is periodic table of elements Group IV、Group V or group vi transition metal，And X is same to each other or different to each other，And X is selected from halogen atom，The alkyl of 1 to 20 carbon atom or alkoxyl，The thiazolinyl of 2 to 20 carbon atoms，The aryl of 6 to 20 carbon atoms、Alkylaryl、Aryl alkyl、The group of aryloxy group.

Description

Metallocene compound, the carbon monoxide-olefin polymeric comprising metallocene compound and use The olefine polymerizing process of metallocene compound

Invention field

The present invention relates to metallocene compound, and more particularly, to can be with high polymerization activity Polymerization Alkene polymerization thing Or the metallocene compound of copolymer, and include the carbon monoxide-olefin polymeric of described metallocene compound, and use described cyclopentadienyl gold Belong to the olefine polymerizing process of compound.

Background of invention

The catalyst with transition metal is widely used in olefinic polymerization.Such as, the 2nd, 608,933 and 3,007, No. 725 The metallocene compound of 4B group 4 transition metal and cyclopentadiene part that German Patent Publication has a periodic table of elements can serve as The catalyst of the olefin polymerization in the presence of the activator of such as MAO, described transition metal such as zirconium, titanium, hafnium. The example of cyclopentadiene part includes substituted or unsubstituted cyclopentadienyl group, indenyl, fluorenyl etc..Multiple have cyclopentadienyl group The metallocene compound of part has been used as olefin polymerization catalysis.Furthermore it is known that the chemical constitution of metallocene compound is to conduct The suitability of the metallocene of catalyst has appreciable impact.Such as, size and the position of the substituent group of cyclopentadienyl rings it are connected to Put the activity to catalyst, solid-specificity and stability and the physical property etc. of polymer that obtained by catalyst has Appreciable impact.There is zirconium and the example of the metallocene compound of cyclopentadienyl ligands replaced by alkyl includes double (alkyl ring Pentadienyl) zirconium dichloride (wherein, alkyl represents methyl, ethyl, isopropyl, the tert-butyl group, trimethyl silyl etc.) (J.Chem.Soc.Dalton Trans., 805 (1981)), double (pentamethylcyclopentadiene base) zirconium dichloride (J.Amer.Chem.Soc., 100,3078 (1978)), (pentamethylcyclopentadiene base) (cyclopentadienyl group) zirconium dichloride (J.Amer.Chem.Soc., 106,6355 (1984)), double (two, tri or tetra-alkyl-cyclopentadienyl group) zirconium dichloride (the 4th, No. 874,880 United States Patent (USP)s) etc..Additionally, have the non-crosslinked metallocene compound the (the 5th, 780,659 of substituted indenyl ligands Number United States Patent (USP)), there is the metallocene compound the (the 4,312,270th of the cyclopentadienyl ligands replaced by mono alkyl substituent group Number Deutsche Bundespatent) it is known.

In recent years, for instance it is known to include the metallocene that the zirconium by substituted cyclopentadienyl ligands with as transition metal forms The catalyst system and catalyzing (compositions) of compound and MAO has activity (No. 129,368 Europe of excellence in olefin polymerization Continent patent, the 4th, 874, No. 880 and the 5th, 324, No. 800 United States Patent (USP), Makromol.Chem.Rapid Commun., 4,417 (1983) etc.).It is also known that by having the alkyl as part and/or the metallocene compound of halogen atom and aikyiaiurnirsoxan beta group The caltalyst become ties up to have in polymerization of Alpha-olefin high activity, and be made up of metallocene compound and organoboron compound Caltalyst ties up to also have high activity (Macromolecules 1993,26,3239 in polymerization of Alpha-olefin;J,Am, chem.Soc.1991,113,3623)。

Furthermore it is known that include that the caltalyst of metallocene compound and aikyiaiurnirsoxan beta or organoboron compound ties up to 60 ° of C extremely Under the polymerization temperature of 90 ° of C, there is most highly active.But, although the initial activity of catalyst is the highest, but catalyst At high temperature instability, and their activity reduces with polymerization time.Therefore, polymerization productivity reduces, then for preparing is poly- The degradation of compound, and the polymer prepared is unsuitable for preparing various plastic article.If polymerization temperature reduces, then prepare The molecular weight of polymer may increase, but catalysis activity reduces, thus can not obtain enough polymerization activities.

Invention summary

Novel metallocene compound that the present inventor is prepared for having high polymerization activity and include described novel cyclopentadienyl gold Belong to the catalyst system for olefinic polymerization of compound, and also have been developed for using described catalyst system to prepare polyolefin Method.

Therefore, it is an object of the present invention to provide the metallocene compound for olefinic polymerization, its catalysis activity and Stability is excellent the most at high polymerization temperatures.Keep the catalysis activity of metallocene compound for a long time, and use cyclopentadienyl Metallic compound stably prepares the polymer with preferred performance.

Another object of the present invention is to provide the metallocene compound for olefinic polymerization, it has various performance, and The polyolefin with superior polymers form can be polymerized.

Offer is provided and for the metallocene compound of olefinic polymerization and includes described metallocene The carbon monoxide-olefin polymeric of compound and use the olefine polymerizing process of described metallocene compound, described metallocene compound can hold Change places the polymer of the preparation controlled in homogeneous polymerization medium (solution phase) or non-homogeneous polymerisation medium (gas phase or slurry phase) Molecular weight.

In order to realize these and other objects, the invention provides the cyclopentadienyl for olefinic polymerization represented by general formula 1 Metallic compound,

[formula 1]

(4HInd)(Cp’)MX₂

Wherein, 4HInd is the group with tetrahydro indenyl core, and Cp ' is the group with cyclopentadienyl group core, and 4HInd and Cp ' can be unsubstituted or be substituted with one or more substituents.Substituent group can be same to each other or different to each other, and And be the alkyl selected from 1 to 20 carbon atom, alkoxyl, aIkylsilyl groups, alkyl siloxy, alkyl amino or halo Alkyl；The cycloalkyl of 3 to 20 carbon atoms；The aryl of 6 to 20 carbon atoms, aryl alkyl, arylsilyl groups, alkylaryl Or aryloxy group；The dialkyl amido of 2 to 20 carbon atoms；Halogen atom；And the group of amino.M be periodic table of elements Group IV, Group V or the transition metal of group vi.X can be same to each other or different to each other, and is selected from halogen atom；1 to 20 carbon atom Alkyl or alkoxyl；The thiazolinyl of 2 to 20 carbon atoms；The aryl of 6 to 20 carbon atoms, alkylaryl, aryl alkyl, aryloxy group Group.

Present invention also offers olefin Polymerization catalyst compositions, it includes metallocene compound and activator, or by Metallocene compound that organic or inorganic is carrier loaded and activator.Present invention also offers olefine polymerizing process, it is included in The step of at least one alkene it is polymerized in the presence of polymerization catalyst composition.

Different from the conventional catalyst that polymerization activity reduces with polymerization time, the carbon monoxide-olefin polymeric of the present invention has holding Constant high polymerization activity.Therefore, during commercial polymerization, the productivity ratio of the carbon monoxide-olefin polymeric of the present invention is excellent. Additionally, the multiple metallocene compound of the application of the invention, can be in homogeneous (solution) or heterogeneous (gas or slurry) polymerization During preparation there is olefin polymer or the copolymer of multiple performance.Additionally, use the carbon monoxide-olefin polymeric of the present invention, can hold Change places and control olefin polymer or the molecular weight of copolymer, molecular weight distribution and the composition distribution of preparation.

Detailed Description Of The Invention

Enclosed by the more complete understanding and many thereof that the present invention be will be better appreciated with reference to detailed description below Advantage.

The metallocene compound of the present invention is the catalyst for olefinic polymerization, and it includes having tetrahydro indenyl core (4HInd) part, the part with cyclopentadienyl group core (Cp ') and the transition metal (M) being connected with part, and by formula 1 represents.

[formula 1]

(4HInd)(Cp’)MX₂

In formula 1,4HInd is the group with tetrahydro indenyl core (part), such as, have 4,5,6,7-tetrahydro indenyls The group of core, and Cp ' is the group with cyclopentadienyl group core, it is however preferred to have such as cyclopentadienyl group, indenyl, fluorenyl, The group of the cyclopentadienyl group core of azulenyl etc..4HInd and Cp ' can be unsubstituted or substituted.In detail, 4HInd can be by 1 Partly replacing to 11 substituent groups, and Cp ' can be one or more, such as 1 to 5 substituent group partly replaces.Take Can be same to each other or different to each other for base, and be the alkyl selected from 1 to 20 carbon atom, alkoxyl, aIkylsilyl groups, alkyl Siloxy, alkyl amino or haloalkyl, the cycloalkyl of 3 to 20 carbon atoms, the aryl of 6 to 20 carbon atoms, aryl Alkyl, arylsilyl groups, alkylaryl or aryloxy group, the dialkyl amido of 2 to 20 carbon atoms, halogen atom and amino Group.M is the Group IV of the periodic table of elements, group V or group vi transition metal, is preferably selected from the titanium of Group IV, zirconium and hafnium One or more transition metal.X can be same to each other or different to each other, and is selected from halogen atom, the alkyl of 1 to 20 carbon atom Or alkoxyl, the thiazolinyl of 2 to 20 carbon atoms, the group of the aryl of 6 to 20 carbon atoms, alkylaryl or aryloxy group, described Halogen atom is selected from fluorine, chlorine, bromine, iodine etc..

The metallocene compound that can individually or represent with the form use formula 1 of its two or more mixture.Metallocene The limiting examples of compound includes (4,5,6,7-tetrahydro indenyl) (indenyl) titanium chloride, (4,5,6,7-tetrahydro indenyl) (indenyl) zirconium dichloride, (4,5,6,7-tetrahydro indenyl) (indenyl) hafnium dichloride, (4,5,6,7-tetrahydro indenyl) (indenyl) difluoro Change titanium, (4,5,6,7-tetrahydro indenyl) (indenyl) zirconium difluoride, (4,5,6,7-tetrahydro indenyl) (indenyl) bifluoride hafnium, (4,5, 6,7-tetrahydro indenyl) (indenyl) dibrominated titanium, (4,5,6,7-tetrahydro indenyl) (indenyl) dibrominated zirconium, (4,5,6,7-tetrahydroindene Base) (indenyl) dibrominated hafnium, (4,5,6,7-tetrahydro indenyl) (indenyl) diiodinating titanium, (4,5,6,7-tetrahydro indenyl) (indenyl) two Iodate zirconium, (4,5,6,7-tetrahydro indenyl) (indenyl) diiodinating hafnium, (1-methyl-4,5,6,7-tetrahydro indenyl) (indenyl) dichloride Titanium, (1-methyl-4,5,6,7-tetrahydro indenyl) (indenyl) zirconium dichloride, (1-methyl-4,5,6,7-tetrahydro indenyl) (indenyl) two Hafnium chloride, (1-methyl-4,5,6,7-tetrahydro indenyl) (indenyl) bifluoride titanium, (1-methyl-4,5,6,7-tetrahydro indenyl) (indenes Base) zirconium difluoride, (1-methyl-4,5,6,7-tetrahydro indenyl) (indenyl) bifluoride hafnium, (1-methyl-4,5,6,7-tetrahydro indenyl) (indenyl) dibrominated titanium, (1-methyl-4,5,6,7-tetrahydro indenyl) (indenyl) dibrominated zirconium, (1-methyl-4,5,6,7-tetrahydroindene Base) (indenyl) dibrominated hafnium, (1-methyl-4,5,6,7-tetrahydro indenyl) (indenyl) diiodinating titanium, (1-methyl-4,5,6,7-four Hydrogen indenyl) (indenyl) diiodinating zirconium, (1-methyl-4,5,6,7-tetrahydro indenyl) (indenyl) diiodinating hafnium, (4,5,6,7-tetrahydroindene Base) (1-methylindenyl) titanium chloride, (4,5,6,7-tetrahydro-indenyl) (1-methylindenyl) zirconium dichloride, (4,5,6,7-tetrahydrochysene Indenyl) (1-methylindenyl) hafnium dichloride, (4,5,6,7-tetrahydro indenyl) (1-methylindenyl) bifluoride titanium, (4,5,6,7-tetra- Hydrogen indenyl) (1-methylindenyl) zirconium difluoride, (4,5,6,7-tetrahydro indenyl) (1-methylindenyl) bifluoride hafnium, (4,5,6,7- Tetrahydro indenyl) (1-methylindenyl) dibrominated titanium, (4,5,6,7-tetrahydro indenyl) (1-methylindenyl) dibrominated zirconium, (4,5,6, 7-tetrahydro indenyl) (1-methylindenyl) dibrominated hafnium, (4,5,6,7-tetrahydro indenyl) (1-methylindenyl) diiodinating titanium, (4,5, 6,7-tetrahydro indenyl) (1-methylindenyl) diiodinating zirconium, (4,5,6,7-tetrahydro indenyl) (1-methylindenyl) diiodinating hafnium, (2- Methyl-4,5,6,7-tetrahydro indenyl) (indenyl) titanium chloride, (2-methyl-4,5,6,7-tetrahydro indenyl) (indenyl) zirconium dichloride, (2-methyl-4,5,6,7-tetrahydro indenyl) (indenyl) hafnium dichloride, (2-methyl-4,5,6,7-tetrahydro indenyl) (indenyl) bifluoride Titanium, (2-methyl-4,5,6,7-tetrahydro indenyl) (indenyl) zirconium difluoride, (2-methyl-4,5,6,7-tetrahydro indenyl) (indenyl) two Hafnium fluoride, (2-methyl-4,5,6,7-tetrahydro indenyl) (indenyl) dibrominated titanium, (2-methyl-4,5,6,7-tetrahydro indenyl) (indenes Base) dibrominated zirconium, (2-methyl-4,5,6,7-tetrahydro indenyl) (indenyl) dibrominated hafnium, (2-methyl-4,5,6,7-tetrahydro indenyl) (indenyl) diiodinating titanium, (2-methyl-4,5,6,7-tetrahydro indenyl) (indenyl) diiodinating zirconium, (2-methyl-4,5,6,7-tetrahydroindene Base) (indenyl) diiodinating hafnium, (4,5,6,7-tetrahydro indenyl) (2-methylindenyl) titanium chloride, (4,5,6,7-tetrahydro indenyl) (2-methylindenyl) zirconium dichloride, (4,5,6,7-tetrahydro indenyl) (2-methylindenyl) hafnium dichloride, (4,5,6,7-tetrahydroindene Base) (2-methylindenyl) bifluoride titanium, (4,5,6,7-tetrahydro indenyl) (2-methylindenyl) zirconium difluoride, (4,5,6,7-tetrahydrochysene Indenyl) (2-methylindenyl) bifluoride hafnium, (4,5,6,7-tetrahydro indenyl) (2-methylindenyl) dibrominated titanium, (4,5,6,7-tetra- Hydrogen indenyl) (2-methylindenyl) dibrominated zirconium, (4,5,6,7-tetrahydro indenyl) (2-methylindenyl) dibrominated hafnium, (4,5,6,7- Tetrahydro indenyl) (2-methylindenyl) diiodinating titanium, (4,5,6,7-tetrahydro indenyl) (2-methylindenyl) diiodinating zirconium, (4,5,6, 7-tetrahydro indenyl) (2-methylindenyl) diiodinating hafnium, (1-ethyl-4,5,6,7-tetrahydro indenyl) (indenyl) zirconium dichloride, (1-second Base-4,5,6,7-tetrahydro indenyl) (indenyl) hafnium dichloride, (1-ethyl-4,5,6,7-tetrahydro indenyl) (indenyl) bifluoride titanium, (1-ethyl-4,5,6,7-tetrahydro indenyl) (indenyl) zirconium difluoride, (1-ethyl-4,5,6,7-tetrahydro indenyl) (indenyl) bifluoride Hafnium, (1-ethyl-4,5,6,7-tetrahydro indenyl) (indenyl) dibrominated titanium, (1-ethyl-4,5,6,7-tetrahydro indenyl) (indenyl) two Zirconium bromide, (1-ethyl-4,5,6,7-tetrahydro indenyl) (indenyl) dibrominated hafnium, (1-ethyl-4,5,6,7-tetrahydro indenyl) (indenes Base) diiodinating titanium, (1-ethyl-4,5,6,7-tetrahydro indenyl) (indenyl) diiodinating zirconium, (1-ethyl-4,5,6,7-tetrahydro indenyl) (indenyl) diiodinating hafnium, (4,5,6,7-tetrahydro indenyl) (1-ethyl-indenyl) titanium chloride, (4,5,6,7-tetrahydro indenyl) (1-second Base indenyl) zirconium dichloride, (4,5,6,7-tetrahydro indenyl) (1-ethyl-indenyl) hafnium dichloride, (4,5,6,7-tetrahydro indenyl) (1- Ethyl-indenyl) bifluoride titanium, (4,5,6,7-tetrahydro indenyl) (1-ethyl-indenyl) zirconium difluoride, (4,5,6,7-tetrahydro indenyl) (1-ethyl-indenyl) bifluoride hafnium, (4,5,6,7-tetrahydro indenyl) (1-ethyl-indenyl) dibrominated titanium, (4,5,6,7-tetrahydroindene Base) (1-ethyl-indenyl) dibrominated zirconium, (4,5,6,7-tetrahydro indenyl) (1-ethyl-indenyl) dibrominated hafnium, (4,5,6,7-tetrahydrochysene Indenyl) (1-ethyl-indenyl) diiodinating titanium, (4,5,6,7-tetrahydro indenyl) (1-ethyl-indenyl) diiodinating zirconium, (4,5,6,7-tetra- Hydrogen indenyl) (1-ethyl-indenyl) diiodinating hafnium, (2-ethyl-4,5,6,7-tetrahydro indenyl) (indenyl) titanium chloride, (2-ethyl- 4,5,6,7-tetrahydro indenyl) (indenyl) zirconium dichloride, (2-ethyl-4,5,6,7-tetrahydro indenyl) (indenyl) hafnium dichloride, (2-second Base-4,5,6,7-tetrahydro indenyl) (indenyl) bifluoride titanium, (2-ethyl-4,5,6,7-tetrahydro indenyl) (indenyl) zirconium difluoride, (2-ethyl-4,5,6,7-tetrahydro indenyl) (indenyl) bifluoride hafnium, (2-ethyl-4,5,6,7-tetrahydro indenyl) (indenyl) dibrominated Titanium, (2-ethyl-4,5,6,7-tetrahydro indenyl) (indenyl) dibrominated zirconium, (2-ethyl-4,5,6,7-tetrahydro indenyl) (indenyl) two Bromination hafnium, (2-ethyl-4,5,6,7-tetrahydro indenyl) (indenyl) diiodinating titanium, (2-ethyl-4,5,6,7-tetrahydro indenyl) (indenes Base) diiodinating zirconium, (2-ethyl-4,5,6,7-tetrahydro indenyl) (indenyl) diiodinating hafnium, (4,5,6,7-tetrahydro indenyl) (2-ethyl Indenyl) titanium chloride, (4,5,6,7-tetrahydro indenyl) (2-ethyl-indenyl) zirconium dichloride, (4,5,6,7-tetrahydro indenyl) (2-second Base indenyl) hafnium dichloride, (4,5,6,7-tetrahydro indenyl) (2-ethyl-indenyl) bifluoride titanium, (4,5,6,7-tetrahydro indenyl) (2- Ethyl-indenyl) zirconium difluoride, (4,5,6,7-tetrahydro indenyl) (2-ethyl-indenyl) bifluoride hafnium, (4,5,6,7-tetrahydro indenyl) (2-ethyl-indenyl) dibrominated titanium, (4,5,6,7-tetrahydro indenyl) (2-ethyl-indenyl) dibrominated zirconium, (4,5,6,7-tetrahydroindene Base) (2-ethyl-indenyl) dibrominated hafnium, (4,5,6,7-tetrahydro indenyl) (2-ethyl-indenyl) diiodinating titanium, (4,5,6,7-tetrahydrochysene Indenyl) (2-ethyl-indenyl) diiodinating zirconium, (4,5,6,7-tetrahydro indenyl) (2-ethyl-indenyl) diiodinating hafnium, (1-propyl group-4,5, 6,7-tetrahydro indenyl) (indenyl) zirconium dichloride, (1-propyl group-4,5,6,7-tetrahydro indenyl) (indenyl) hafnium dichloride, (1-propyl group- 4,5,6,7-tetrahydro indenyl) (indenyl) bifluoride titanium, (1-propyl group-4,5,6,7-tetrahydro indenyl) (indenyl) zirconium difluoride, (1- Propyl group-4,5,6,7-tetrahydro indenyl) (indenyl) bifluoride hafnium, (1-propyl group-4,5,6,7-tetrahydro indenyl) (indenyl) dibrominated titanium, (1-propyl group-4,5,6,7-tetrahydro indenyl) (indenyl) dibrominated zirconium, (1-propyl group-4,5,6,7-tetrahydro indenyl) (indenyl) dibrominated Hafnium, (1-propyl group-4,5,6,7-tetrahydro indenyl) (indenyl) diiodinating titanium, (1-propyl group-4,5,6,7-tetrahydro indenyl) (indenyl) two Iodate zirconium, (1-propyl group-4,5,6,7-tetrahydro indenyl) (indenyl) diiodinating hafnium, (4,5,6,7-tetrahydro indenyl) (1-propyl group indenyl) Titanium chloride, (4,5,6,7-tetrahydro indenyl) (1-propyl group indenyl) zirconium dichloride, (4,5,6,7-tetrahydro indenyl) (1-propyl group indenes Base) hafnium dichloride, (4,5,6,7-tetrahydro indenyl) (1-propyl group indenyl) bifluoride titanium, (4,5,6,7-tetrahydro indenyl) (1-propyl group Indenyl) zirconium difluoride, (4,5,6,7-tetrahydro indenyl) (1-propyl group indenyl) bifluoride hafnium, (4,5,6,7-tetrahydro indenyl) (1-third Base indenyl) dibrominated titanium, (4,5,6,7-tetrahydro indenyl) (1-propyl group indenyl) dibrominated zirconium, (4,5,6,7-tetrahydro indenyl) (1- Propyl group indenyl) dibrominated hafnium, (4,5,6,7-tetrahydro indenyl) (1-propyl group indenyl) diiodinating titanium, (4,5,6,7-tetrahydro indenyl) (1-propyl group indenyl) diiodinating zirconium, (4,5,6,7-tetrahydro indenyl) (1-propyl group indenyl) diiodinating hafnium, (2-propyl group-4,5,6,7- Tetrahydro indenyl) (indenyl) titanium chloride, (2-propyl group-4,5,6,7-tetrahydro indenyl) (indenyl) zirconium dichloride, (2-propyl group-4,5, 6,7-tetrahydro indenyl) (indenyl) hafnium dichloride, (2-propyl group-4,5,6,7-tetrahydro indenyl) (indenyl) bifluoride titanium, (2-propyl group- 4,5,6,7-tetrahydro indenyl) (indenyl) zirconium difluoride, (2-propyl group-4,5,6,7-tetrahydro indenyl) (indenyl) bifluoride hafnium, (2-third Base-4,5,6,7-tetrahydro indenyl) (indenyl) dibrominated titanium, (2-propyl group-4,5,6,7-tetrahydro indenyl) (indenyl) dibrominated zirconium, (2-propyl group-4,5,6,7-tetrahydro indenyl) (indenyl) dibrominated hafnium, (2-propyl group-4,5,6,7-tetrahydro indenyl) (indenyl) are diiodinating Titanium, (2-propyl group-4,5,6,7-tetrahydro indenyl) (indenyl) diiodinating zirconium, (2-propyl group-4,5,6,7-tetrahydro indenyl) (indenyl) two Iodate hafnium, (4,5,6,7-tetrahydro indenyl) (2-propyl group indenyl) titanium chloride, (4,5,6,7-tetrahydro indenyl) (2-propyl group indenyl) Zirconium dichloride, (4,5,6,7-tetrahydro indenyl) (2-propyl group indenyl) hafnium dichloride, (4,5,6,7-tetrahydro indenyl) (2-propyl group indenes Base) bifluoride titanium, (4,5,6,7-tetrahydro indenyl) (2-propyl group indenyl) zirconium difluoride, (4,5,6,7-tetrahydro indenyl) (2-propyl group Indenyl) bifluoride hafnium, (4,5,6,7-tetrahydro indenyl) (2-propyl group indenyl) dibrominated titanium, (4,5,6,7-tetrahydro indenyl) (2-third Base indenyl) dibrominated zirconium, (4,5,6,7-tetrahydro indenyl) (2-propyl group indenyl) dibrominated hafnium, (4,5,6,7-tetrahydro indenyl) (2- Propyl group indenyl) diiodinating titanium, (4,5,6,7-tetrahydro indenyl) (2-propyl group indenyl) diiodinating zirconium, (4,5,6,7-tetrahydro indenyl) (2-propyl group indenyl) diiodinating hafnium, (1-isopropyl-4,5,6,7-tetrahydro indenyl) (indenyl) zirconium dichloride, (1-isopropyl-4,5, 6,7-tetrahydro indenyl) (indenyl) hafnium dichloride, (1-isopropyl-4,5,6,7-tetrahydro indenyl) (indenyl) bifluoride titanium, (1-isopropyl Base-4,5,6,7-tetrahydro indenyl) (indenyl) zirconium difluoride, (1-isopropyl-4,5,6,7-tetrahydro indenyl) (indenyl) bifluoride Hafnium, (1-isopropyl-4,5,6,7-tetrahydro indenyl) (indenyl) dibrominated titanium, (1-isopropyl-4,5,6,7-tetrahydro indenyl) (indenes Base) dibrominated zirconium, (1-isopropyl-4,5,6,7-tetrahydro indenyl) (indenyl) dibrominated hafnium, (1-isopropyl-4,5,6,7-tetrahydrochysene Indenyl) (indenyl) diiodinating titanium, (1-isopropyl-4,5,6,7-tetrahydro indenyl) (indenyl) diiodinating zirconium, (1-isopropyl-4,5, 6,7-tetrahydro indenyl) (indenyl) diiodinating hafnium, (4,5,6,7-tetrahydro indenyl) (1-isopropylindenyl) titanium chloride, (4,5,6, 7-tetrahydro indenyl) (1-isopropylindenyl) zirconium dichloride, (4,5,6,7-tetrahydro indenyl) (1-isopropylindenyl) hafnium dichloride, (4,5,6,7-tetrahydro indenyl) (1-isopropylindenyl) bifluoride titanium, (4,5,6,7-tetrahydro indenyl) (1-isopropylindenyl) difluoro Change zirconium, (4,5,6,7-tetrahydro indenyl) (1-isopropylindenyl) bifluoride hafnium, (4,5,6,7-tetrahydro indenyl) (1-isopropyl indenes Base) dibrominated titanium, (4,5,6,7-tetrahydro indenyl) (1-isopropylindenyl) dibrominated zirconium, (4,5,6,7-tetrahydro indenyl) (1-is different Propyl group indenyl) dibrominated hafnium, (4,5,6,7-tetrahydro indenyl) (1-isopropylindenyl) diiodinating titanium, (4,5,6,7-tetrahydro indenyl) (1-isopropylindenyl) diiodinating zirconium, (4,5,6,7-tetrahydro indenyl) (1-isopropylindenyl) diiodinating hafnium, (2-isopropyl-4, 5,6,7-tetrahydro indenyl) (indenyl) titanium chloride, (2-isopropyl-4,5,6,7-tetrahydro indenyl) (indenyl) zirconium dichloride, (2-is different Propyl group-4,5,6,7-tetrahydro indenyl) (indenyl) hafnium dichloride, (2-isopropyl-4,5,6,7-tetrahydro indenyl) (indenyl) bifluoride Titanium, (2-isopropyl-4,5,6,7-tetrahydro indenyl) (indenyl) zirconium difluoride, (2-isopropyl-4,5,6,7-tetrahydro indenyl) (indenes Base) bifluoride hafnium, (2-isopropyl-4,5,6,7-tetrahydro indenyl) (indenyl) dibrominated titanium, (2-isopropyl-4,5,6,7-tetrahydrochysene Indenyl) (indenyl) dibrominated zirconium, (2-isopropyl-4,5,6,7-tetrahydro indenyl) (indenyl) dibrominated hafnium, (2-isopropyl-4,5, 6,7-tetrahydro indenyl) (indenyl) diiodinating titanium, (2-isopropyl-4,5,6,7-tetrahydro indenyl) (indenyl) diiodinating zirconium, (2-isopropyl Base-4,5,6,7-tetrahydro indenyl) (indenyl) diiodinating hafnium, (4,5,6,7-tetrahydro indenyl) (2-isopropylindenyl) titanium chloride, (4,5,6,7-tetrahydro indenyl) (2-isopropylindenyl) zirconium dichloride, (4,5,6,7-tetrahydro indenyl) (2-isopropylindenyl) dichloro Change hafnium, (4,5,6,7-tetrahydro indenyl) (2-isopropylindenyl) bifluoride titanium, (4,5,6,7-tetrahydro indenyl) (2-isopropyl indenes Base) zirconium difluoride, (4,5,6,7-tetrahydro indenyl) (2-isopropylindenyl) bifluoride hafnium, (4,5,6,7-tetrahydro indenyl) (2-is different Propyl group indenyl) dibrominated titanium, (4,5,6,7-tetrahydro indenyl) (2-isopropylindenyl) dibrominated zirconium, (4,5,6,7-tetrahydro indenyl) (2-isopropylindenyl) dibrominated hafnium, (4,5,6,7-tetrahydro indenyl) (2-isopropylindenyl) diiodinating titanium, (4,5,6,7-tetrahydrochysene Indenyl) (2-isopropylindenyl) diiodinating zirconium, (4,5,6,7-tetrahydro indenyl) (2-isopropylindenyl) diiodinating hafnium, (the positive fourth of 1- Base-4,5,6,7-tetrahydro indenyl) (indenyl) zirconium dichloride, (1-normal-butyl-4,5,6,7-tetrahydro indenyl) (indenyl) hafnium dichloride, (1-normal-butyl-4,5,6,7-tetrahydro indenyl) (indenyl) bifluoride titanium, (1-normal-butyl-4,5,6,7-tetrahydro indenyl) (indenyl) Zirconium difluoride, (1-normal-butyl-4,5,6,7-tetrahydro indenyl) (indenyl) bifluoride hafnium, (1-normal-butyl-4,5,6,7-tetrahydroindene Base) (indenyl) dibrominated titanium, (1-normal-butyl-4,5,6,7-tetrahydro indenyl) (indenyl) dibrominated zirconium, (1-normal-butyl-4,5,6, 7-tetrahydro indenyl) (indenyl) dibrominated hafnium, (1-normal-butyl-4,5,6,7-tetrahydro indenyl) (indenyl) diiodinating titanium, (the positive fourth of 1- Base-4,5,6,7-tetrahydro indenyl) (indenyl) diiodinating zirconium, (1-normal-butyl-4,5,6,7-tetrahydro indenyl) (indenyl) diiodinating hafnium, (4,5,6,7-tetrahydro indenyl) (1-normal-butyl indenyl) titanium chloride, (4,5,6,7-tetrahydro indenyl) (1-normal-butyl indenyl) dichloro Change zirconium, (4,5,6,7-tetrahydro indenyl) (1-normal-butyl indenyl) hafnium dichloride, (4,5,6,7-tetrahydro indenyl) (1-propyl group indenyl) Bifluoride titanium, (4,5,6,7-tetrahydro indenyl) (1-normal-butyl indenyl) zirconium difluoride, (4,5,6,7-tetrahydro indenyl) (1-normal-butyl Indenyl) bifluoride hafnium, (4,5,6,7-tetrahydro indenyl) (1-normal-butyl indenyl) dibrominated titanium, (4,5,6,7-tetrahydro indenyl) (1- Normal-butyl indenyl) dibrominated zirconium, (4,5,6,7-tetrahydro indenyl) (1-normal-butyl indenyl) dibrominated hafnium, (4,5,6,7-tetrahydroindene Base) (1-normal-butyl indenyl) diiodinating titanium, (4,5,6,7-tetrahydro indenyl) (1-normal-butyl indenyl) diiodinating zirconium, (4,5,6,7- Tetrahydro indenyl) (1-normal-butyl indenyl) diiodinating hafnium, (2-normal-butyl-4,5,6,7-tetrahydro indenyl) (indenyl) titanium chloride, (2- Normal-butyl-4,5,6,7-tetrahydro indenyl) (indenyl) zirconium dichloride, (2-normal-butyl-4,5,6,7-tetrahydro indenyl) (indenyl) dichloro Change hafnium, (2-normal-butyl-4,5,6,7-tetrahydro indenyl) (indenyl) bifluoride titanium, (2-normal-butyl-4,5,6,7-tetrahydro indenyl) (indenes Base) zirconium difluoride, (2-normal-butyl-4,5,6,7-tetrahydro indenyl) (indenyl) bifluoride hafnium, (2-normal-butyl-4,5,6,7-tetrahydrochysene Indenyl) (indenyl) dibrominated titanium, (2-normal-butyl-4,5,6,7-tetrahydro indenyl) (indenyl) dibrominated zirconium, (2-normal-butyl-4,5, 6,7-tetrahydro indenyl) (indenyl) dibrominated hafnium, (2-normal-butyl-4,5,6,7-tetrahydro indenyl) (indenyl) diiodinating titanium, (the positive fourth of 2- Base-4,5,6,7-tetrahydro indenyl) (indenyl) diiodinating zirconium, (2-normal-butyl-4,5,6,7-tetrahydro indenyl) (indenyl) diiodinating hafnium, (4,5,6,7-tetrahydro indenyl) (2-normal-butyl indenyl) titanium chloride, (4,5,6,7-tetrahydro indenyl) (2-normal-butyl indenyl) dichloro Change zirconium, (4,5,6,7-tetrahydro indenyl) (2-normal-butyl indenyl) hafnium dichloride, (4,5,6,7-tetrahydro indenyl) (2-normal-butyl indenes Base) bifluoride titanium, (4,5,6,7-tetrahydro indenyl) (2-normal-butyl indenyl) zirconium difluoride, (4,5,6,7-tetrahydro indenyl) (2-is just Butyl indenyl) bifluoride hafnium, (4,5,6,7-tetrahydro indenyl) (2-normal-butyl indenyl) dibrominated titanium, (4,5,6,7-tetrahydro indenyl) (2-normal-butyl indenyl) dibrominated zirconium, (4,5,6,7-tetrahydro indenyl) (2-normal-butyl indenyl) dibrominated hafnium, (4,5,6,7-tetrahydrochysene Indenyl) (2-normal-butyl indenyl) diiodinating titanium, (4,5,6,7-tetrahydro indenyl) (2-normal-butyl indenyl) diiodinating zirconium, (4,5,6, 7-tetrahydro indenyl) (2-normal-butyl indenyl) diiodinating hafnium, (1-isobutyl group-4,5,6,7-tetrahydro indenyl) (indenyl) zirconium dichloride, (1-isobutyl group-4,5,6,7-tetrahydro indenyl) (indenyl) hafnium dichloride, (1-isobutyl group-4,5,6,7-tetrahydro indenyl) (indenyl) Bifluoride titanium, (1-isobutyl group-4,5,6,7-tetrahydro indenyl) (indenyl) zirconium difluoride, (1-isobutyl group-4,5,6,7-tetrahydroindene Base) (indenyl) bifluoride hafnium, (1-isobutyl group-4,5,6,7-tetrahydro indenyl) (indenyl) dibrominated titanium, (1-isobutyl group-4,5,6, 7-tetrahydro indenyl) (indenyl) dibrominated zirconium, (1-isobutyl group-4,5,6,7-tetrahydro indenyl) (indenyl) dibrominated hafnium, (1-isobutyl Base-4,5,6,7-tetrahydro indenyl) (indenyl) diiodinating titanium, (1-isobutyl group-4,5,6,7-tetrahydro indenyl) (indenyl) diiodinating zirconium, (1-isobutyl group-4,5,6,7-tetrahydro indenyl) (indenyl) diiodinating hafnium, (4,5,6,7-tetrahydro indenyl) (1-isobutyl group indenyl) two Titanium chloride, (4,5,6,7-tetrahydro indenyl) (1-isobutyl group indenyl) zirconium dichloride, (4,5,6,7-tetrahydro indenyl) (1-isobutyl group indenes Base) hafnium dichloride, (4,5,6,7-tetrahydro indenyl) (1-isobutyl group indenyl) bifluoride titanium, (4,5,6,7-tetrahydro indenyl) (1-is different Butyl indenyl) zirconium difluoride, (4,5,6,7-tetrahydro indenyl) (1-isobutyl group indenyl) bifluoride hafnium, (4,5,6,7-tetrahydro indenyl) (1-isobutyl group indenyl) dibrominated titanium, (4,5,6,7-tetrahydro indenyl) (1-isobutyl group indenyl) dibrominated zirconium, (4,5,6,7-tetrahydrochysene Indenyl) (1-isobutyl group indenyl) dibrominated hafnium, (4,5,6,7-tetrahydro indenyl) (1-isobutyl group indenyl) diiodinating titanium, (4,5,6, 7-tetrahydro indenyl) (1-isobutyl group indenyl) diiodinating zirconium, (4,5,6,7-tetrahydro indenyl) (1-isobutyl group indenyl) diiodinating hafnium, (2-isobutyl group-4,5,6,7-tetrahydro indenyl) (indenyl) titanium chloride, (2-isobutyl group-4,5,6,7-tetrahydro indenyl) (indenyl) two Zirconium chloride, (2-isobutyl group-4,5,6,7-tetrahydro indenyl) (indenyl) hafnium dichloride, (2-isobutyl group-4,5,6,7-tetrahydro indenyl) (indenyl) bifluoride titanium, (2-isobutyl group-4,5,6,7-tetrahydro indenyl) (indenyl) zirconium difluoride, (2-isobutyl group-4,5,6,7-four Hydrogen indenyl) (indenyl) bifluoride hafnium, (2-isobutyl group-4,5,6,7-tetrahydro indenyl) (indenyl) dibrominated titanium, (2-isobutyl group-4, 5,6,7-tetrahydro indenyl) (indenyl) dibrominated zirconium, (2-isobutyl group-4,5,6,7-tetrahydro indenyl) (indenyl) dibrominated hafnium, (2-is different Butyl-4,5,6,7-tetrahydro indenyl) (indenyl) diiodinating titanium, (2-isobutyl group-4,5,6,7-tetrahydro indenyl) (indenyl) be diiodinating Zirconium, (2-isobutyl group-4,5,6,7-tetrahydro indenyl) (indenyl) diiodinating hafnium, (4,5,6,7-tetrahydro indenyl) (2-isobutyl group indenyl) Titanium chloride, (4,5,6,7-tetrahydro indenyl) (2-isobutyl group indenyl) zirconium dichloride, (4,5,6,7-tetrahydro indenyl) (2-isobutyl group Indenyl) hafnium dichloride, (4,5,6,7-tetrahydro indenyl) (2-isobutyl group indenyl) bifluoride titanium, (4,5,6,7-tetrahydro indenyl) (2- Isobutyl group indenyl) zirconium difluoride, (4,5,6,7-tetrahydro indenyl) (2-isobutyl group indenyl) bifluoride hafnium, (4,5,6,7-tetrahydroindene Base) (2-isobutyl group indenyl) dibrominated titanium, (4,5,6,7-tetrahydro indenyl) (2-isobutyl group indenyl) dibrominated zirconium, (4,5,6,7- Tetrahydro indenyl) (2-isobutyl group indenyl) dibrominated hafnium, (4,5,6,7-tetrahydro-indenyl) (2-isobutyl group indenyl) diiodinating titanium, (4, 5,6,7-tetrahydro-indenyl) (2-isobutyl group indenyl) diiodinating zirconium, (4,5,6,7-tetrahydro-indenyl) (2-isobutyl group indenyl) diiodo- Change hafnium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) titanium chloride, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) zirconium dichloride, (1-methyl-4,5,6,7-tetrahydro indenyl) (indenyl) hafnium dichloride, (1-methyl-4,5,6,7- Tetrahydro indenyl) (1-methylindenyl) bifluoride titanium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) zirconium difluoride, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) bifluoride hafnium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-first Base indenyl) dibrominated titanium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) dibrominated zirconium, (1-methyl-4,5,6, 7-tetrahydro indenyl) (1-methylindenyl) dibrominated hafnium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) be diiodinating Titanium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) diiodinating zirconium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1- Methylindenyl) diiodinating hafnium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) titanium chloride, (1-methyl-4,5, 6,7-tetrahydro indenyl) (1-methylindenyl) zirconium dichloride, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) dichloride Hafnium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) bifluoride titanium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1- Methylindenyl) zirconium difluoride, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) bifluoride hafnium, (1-methyl-4,5, 6,7-tetrahydro indenyl) (1-methylindenyl) dibrominated titanium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) dibrominated Zirconium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) dibrominated hafnium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1- Methylindenyl) diiodinating titanium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) diiodinating zirconium, (1-methyl-4,5, 6,7-tetrahydro indenyl) (1-methylindenyl) diiodinating hafnium, (2-methyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) dichloride Titanium, (2-methyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) zirconium dichloride, (2-methyl-4,5,6,7-tetrahydro indenyl) (1- Methylindenyl) hafnium dichloride, (2-methyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) bifluoride titanium, (2-methyl-4,5, 6,7-tetrahydro indenyl) (1-methylindenyl) zirconium difluoride, (2-methyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) bifluoride Hafnium, (2-methyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) dibrominated titanium, (2-methyl-4,5,6,7-tetrahydro indenyl) (1- Methylindenyl) dibrominated zirconium, (2-methyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) dibrominated hafnium, (2-methyl-4,5, 6,7-tetrahydro indenyl) (1-methylindenyl) diiodinating titanium, (2-methyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) be diiodinating Zirconium, (2-methyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) diiodinating hafnium, (1-methyl-4,5,6,7-tetrahydro indenyl) (2- Methylindenyl) titanium chloride, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-methylindenyl) zirconium dichloride, (1-methyl-4,5, 6,7-tetrahydro indenyl) (2-methylindenyl) hafnium dichloride, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-methylindenyl) bifluoride Titanium, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-methylindenyl) zirconium difluoride, (1-methyl-4,5,6,7-tetrahydro indenyl) (2- Methylindenyl) bifluoride hafnium, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-methylindenyl) dibrominated titanium, (1-methyl-4,5, 6,7-tetrahydro indenyl) (2-methylindenyl) dibrominated zirconium, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-methylindenyl) dibrominated Hafnium, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-methylindenyl) diiodinating titanium, (1-methyl-4,5,6,7-tetrahydro indenyl) (2- Methylindenyl) diiodinating zirconium, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-methylindenyl) diiodinating hafnium, (1-ethyl-4,5, 6,7-tetrahydro indenyl) (1-methyl-indenyl) zirconium dichloride, (1-ethyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) dichloro Change hafnium, (1-ethyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) bifluoride titanium, (1-ethyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) zirconium difluoride, (1-ethyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) bifluoride hafnium, (1-ethyl-4, 5,6,7-tetrahydro indenyl) (1-methylindenyl) dibrominated titanium, (1-ethyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) dibromo Change zirconium, (1-ethyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) dibrominated hafnium, (1-ethyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) diiodinating titanium, (1-ethyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) diiodinating zirconium, (1-ethyl-4, 5,6,7-tetrahydro indenyl) (1-methylindenyl) diiodinating hafnium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-ethyl-indenyl) dichloro Change titanium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-ethyl-indenyl) zirconium dichloride, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-ethyl-indenyl) hafnium dichloride, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-ethyl-indenyl) bifluoride titanium, (1-methyl-4, 5,6,7-tetrahydro indenyl) (1-ethyl-indenyl) zirconium difluoride, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-ethyl-indenyl) difluoro Change hafnium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-ethyl-indenyl) dibrominated titanium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-ethyl-indenyl) dibrominated zirconium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-ethyl-indenyl) dibrominated hafnium, (1-methyl-4, 5,6,7-tetrahydro indenyl) (1-ethyl-indenyl) diiodinating titanium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-ethyl-indenyl) diiodo- Change zirconium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-ethyl-indenyl) diiodinating hafnium, (2-ethyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) titanium chloride, (2-ethyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) zirconium dichloride, (2-ethyl-4, 5,6,7-tetrahydro indenyl) (1-methylindenyl) hafnium dichloride, (2-ethyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) difluoro Change titanium, (2-ethyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) zirconium difluoride, (2-ethyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) bifluoride hafnium, (2-ethyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) dibrominated titanium, (2-ethyl-4, 5,6,7-tetrahydro indenyl) (1-methylindenyl) dibrominated zirconium, (2-ethyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) dibromo Change hafnium, (2-ethyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) diiodinating titanium, (2-ethyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) diiodinating zirconium, (2-ethyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) diiodinating hafnium, (1-methyl-4, 5,6,7-tetrahydro indenyl) (2-ethyl-indenyl) titanium chloride, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-ethyl-indenyl) two Zirconium chloride, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-ethyl-indenyl) hafnium dichloride, (1-methyl-4,5,6,7-tetrahydroindene Base) (2-ethyl-indenyl) bifluoride titanium, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-ethyl-indenyl) zirconium difluoride, (1-first Base-4,5,6,7-tetrahydro indenyl) (2-ethyl-indenyl) bifluoride hafnium, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-ethyl indenes Base) dibrominated titanium, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-ethyl-indenyl) dibrominated zirconium, (1-methyl-4,5,6,7-four Hydrogen indenyl) (2-ethyl-indenyl) dibrominated hafnium, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-ethyl-indenyl) diiodinating titanium, (1- Methyl-4,5,6,7-tetrahydro indenyl) (2-ethyl-indenyl) diiodinating zirconium, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-ethyl indenes Base) diiodinating hafnium, (1-propyl group-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) zirconium dichloride, (1-propyl group-4,5,6,7-four Hydrogen indenyl) (1-methylindenyl) hafnium dichloride, (1-propyl group-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) bifluoride titanium, (1- Propyl group-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) zirconium difluoride, (1-propyl group-4,5,6,7-tetrahydro indenyl) (1-methyl indenes Base) bifluoride hafnium, (1-propyl group-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) dibrominated titanium, (1-propyl group-4,5,6,7-four Hydrogen indenyl) (1-methylindenyl) dibrominated zirconium, (1-propyl group-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) dibrominated hafnium, (1- Propyl group-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) diiodinating titanium, (1-propyl group-4,5,6,7-tetrahydro indenyl) (1-methyl indenes Base) diiodinating zirconium, (1-propyl group-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) diiodinating hafnium, (1-methyl-4,5,6,7-four Hydrogen indenyl) (1-propyl group indenyl) titanium chloride, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-propyl group indenyl) zirconium dichloride, (1- Methyl-4,5,6,7-tetrahydro indenyl) (1-propyl group indenyl) hafnium dichloride, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-propyl group indenes Base) bifluoride titanium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-propyl group indenyl) zirconium difluoride, (1-methyl-4,5,6,7-four Hydrogen indenyl) (1-propyl group indenyl) bifluoride hafnium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-propyl group indenyl) dibrominated titanium, (1- Methyl-4,5,6,7-tetrahydro indenyl) (1-propyl group indenyl) dibrominated zirconium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-propyl group indenes Base) dibrominated hafnium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-propyl group indenyl) diiodinating titanium, (1-methyl-4,5,6,7-four Hydrogen indenyl) (1-propyl group indenyl) diiodinating zirconium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-propyl group indenyl) diiodinating hafnium, (2- Propyl group-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) titanium chloride, (2-propyl group-4,5,6,7-tetrahydro indenyl) (1-methyl indenes Base) zirconium dichloride, (2-propyl group-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) hafnium dichloride, (2-propyl group-4,5,6,7-four Hydrogen indenyl) (1-methylindenyl) bifluoride titanium, (2-propyl group-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) zirconium difluoride, (2- Propyl group-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) bifluoride hafnium, (2-propyl group-4,5,6,7-tetrahydro indenyl) (1-methyl indenes Base) dibrominated titanium, (2-propyl group-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) dibrominated zirconium, (2-propyl group-4,5,6,7-four Hydrogen indenyl) (1-methylindenyl) dibrominated hafnium, (2-propyl group-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) diiodinating titanium, (2- Propyl group-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) diiodinating zirconium, (2-propyl group-4,5,6,7-tetrahydro indenyl) (1-methyl indenes Base) diiodinating hafnium, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-propyl group indenyl) titanium chloride, (1-methyl-4,5,6,7-four Hydrogen indenyl) (2-propyl group indenyl) zirconium dichloride, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-propyl group indenyl) hafnium dichloride, (1- Methyl-4,5,6,7-tetrahydro indenyl) (2-propyl group indenyl) bifluoride titanium, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-propyl group indenes Base) zirconium difluoride, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-propyl group indenyl) bifluoride hafnium, (1-methyl-4,5,6,7-four Hydrogen indenyl) (2-propyl group indenyl) dibrominated titanium, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-propyl group indenyl) dibrominated zirconium, (1- Methyl-4,5,6,7-tetrahydro indenyl) (2-propyl group indenyl) dibrominated hafnium, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-propyl group indenes Base) diiodinating titanium, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-propyl group indenyl) diiodinating zirconium, (1-methyl-4,5,6,7-four Hydrogen indenyl) (2-propyl group indenyl) diiodinating hafnium, (1-isopropyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) zirconium dichloride, (1-isopropyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) hafnium dichloride, (1-isopropyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) bifluoride titanium, (1-isopropyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) zirconium difluoride, (1-isopropyl Base-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) bifluoride hafnium, (1-isopropyl-4,5,6,7-tetrahydro indenyl) (1-methyl indenes Base) dibrominated titanium, (1-isopropyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) dibrominated zirconium, (1-isopropyl-4,5,6, 7-tetrahydro indenyl) (1-methylindenyl) dibrominated hafnium, (1-isopropyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) be diiodinating Titanium, (1-isopropyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) diiodinating zirconium, (1-isopropyl-4,5,6,7-tetrahydroindene Base) (1-methylindenyl) diiodinating hafnium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-isopropylindenyl) titanium chloride, (1-first Base-4,5,6,7-tetrahydro indenyl) (1-isopropylindenyl) zirconium dichloride, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-isopropyl Indenyl) hafnium dichloride, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-isopropylindenyl) bifluoride titanium, (1-methyl-4,5,6, 7-tetrahydro indenyl) (1-isopropylindenyl) zirconium difluoride, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-isopropylindenyl) difluoro Change hafnium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-isopropylindenyl) dibrominated titanium, (1-methyl-4,5,6,7-tetrahydroindene Base) (1-isopropylindenyl) dibrominated zirconium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-isopropylindenyl) dibrominated hafnium, (1- Methyl-4,5,6,7-tetrahydro indenyl) (1-isopropylindenyl) diiodinating titanium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-isopropyl Base indenyl) diiodinating zirconium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-isopropylindenyl) diiodinating hafnium, (2-isopropyl-4, 5,6,7-tetrahydro indenyl) (1-methylindenyl) titanium chloride, (2-isopropyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) Zirconium dichloride, (2-isopropyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) hafnium dichloride, (2-isopropyl-4,5,6,7-four Hydrogen indenyl) (1-methylindenyl) bifluoride titanium, (2-isopropyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) zirconium difluoride, (2-isopropyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) bifluoride hafnium, (2-isopropyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) dibrominated titanium, (2-isopropyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) dibrominated zirconium, (2-isopropyl Base-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) dibrominated hafnium, (2-isopropyl-4,5,6,7-tetrahydro indenyl) (1-methyl indenes Base) diiodinating titanium, (2-isopropyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) diiodinating zirconium, (2-isopropyl-4,5,6, 7-tetrahydro indenyl) (1-methylindenyl) diiodinating hafnium, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-isopropylindenyl) dichloride Titanium, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-isopropylindenyl) zirconium dichloride, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-isopropylindenyl) hafnium dichloride, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-isopropylindenyl) bifluoride titanium, (1-first Base-4,5,6,7-tetrahydro indenyl) (2-isopropylindenyl) zirconium difluoride, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-isopropyl Indenyl) bifluoride hafnium, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-isopropylindenyl) dibrominated titanium, (1-methyl-4,5,6, 7-tetrahydro indenyl) (2-isopropylindenyl) dibrominated zirconium, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-isopropylindenyl) dibromo Change hafnium, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-isopropylindenyl) diiodinating titanium, (1-methyl-4,5,6,7-tetrahydroindene Base) (2-isopropylindenyl) diiodinating zirconium, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-isopropylindenyl) diiodinating hafnium, (1- Normal-butyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) zirconium dichloride, (1-normal-butyl-4,5,6,7-tetrahydro indenyl) (1-first Base indenyl) hafnium dichloride, (1-normal-butyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) bifluoride titanium, (1-normal-butyl-4, 5,6,7-tetrahydro indenyl) (1-methylindenyl) zirconium difluoride, (1-normal-butyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) two Hafnium fluoride, (1-normal-butyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) dibrominated titanium, (1-normal-butyl-4,5,6,7-tetrahydrochysene Indenyl) (1-methylindenyl) dibrominated zirconium, (1-normal-butyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) dibrominated hafnium, (1- Normal-butyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) diiodinating titanium, (1-normal-butyl-4,5,6,7-tetrahydro indenyl) (1-first Base indenyl) diiodinating zirconium, (1-normal-butyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) diiodinating hafnium, (1-methyl-4,5, 6,7-tetrahydro indenyl) (1-normal-butyl indenyl) titanium chloride, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-normal-butyl indenyl) two Zirconium chloride, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-normal-butyl indenyl) hafnium dichloride, (1-methyl-4,5,6,7-tetrahydroindene Base) (1-propyl group indenyl) bifluoride titanium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-normal-butyl indenyl) zirconium difluoride, (1-first Base-4,5,6,7-tetrahydro indenyl) (1-normal-butyl indenyl) bifluoride hafnium, (1-methyl-4,5,6,7-tetrahydro indenyl) (positive fourth of 1- Base indenyl) dibrominated titanium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-normal-butyl indenyl) dibrominated zirconium, (1-methyl-4,5, 6,7-tetrahydro indenyl) (1-normal-butyl indenyl) dibrominated hafnium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-normal-butyl indenyl) two Titanium iodide, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-normal-butyl indenyl) diiodinating zirconium, (1-methyl-4,5,6,7-tetrahydroindene Base) (1-normal-butyl indenyl) diiodinating hafnium, (2-normal-butyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) titanium chloride, (2- Normal-butyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) zirconium dichloride, (2-normal-butyl-4,5,6,7-tetrahydro indenyl) (1-first Base indenyl) hafnium dichloride, (2-normal-butyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) bifluoride titanium, (2-normal-butyl-4, 5,6,7-tetrahydro indenyl) (1-methylindenyl) zirconium difluoride, (2-normal-butyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) two Hafnium fluoride, (2-normal-butyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) dibrominated titanium, (2-normal-butyl-4,5,6,7-tetrahydrochysene Indenyl) (1-methylindenyl) dibrominated zirconium, (2-normal-butyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) dibrominated hafnium, (2- Normal-butyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) diiodinating titanium, (2-normal-butyl-4,5,6,7-tetrahydro indenyl) (1-first Base indenyl) diiodinating zirconium, (2-normal-butyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) diiodinating hafnium, (1-methyl-4,5, 6,7-tetrahydro indenyl) (2-normal-butyl indenyl) titanium chloride, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-normal-butyl indenyl) two Zirconium chloride, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-normal-butyl indenyl) hafnium dichloride, (1-methyl-4,5,6,7-tetrahydroindene Base) (2-normal-butyl indenyl) bifluoride titanium, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-normal-butyl indenyl) zirconium difluoride, (1- Methyl-4,5,6,7-tetrahydro indenyl) (2-normal-butyl indenyl) bifluoride hafnium, (1-methyl-4,5,6,7-tetrahydro indenyl) (positive fourth of 2- Base indenyl) dibrominated titanium, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-normal-butyl indenyl) dibrominated zirconium, (1-methyl-4,5, 6,7-tetrahydro indenyl) (2-normal-butyl indenyl) dibrominated hafnium, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-normal-butyl indenyl) two Titanium iodide, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-normal-butyl indenyl) diiodinating zirconium, (1-methyl-4,5,6,7-tetrahydroindene Base) (2-normal-butyl indenyl) diiodinating hafnium, (1-isobutyl group-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) zirconium dichloride, (1- Isobutyl group-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) hafnium dichloride, (1-isobutyl group-4,5,6,7-tetrahydro indenyl) (1-first Base indenyl) bifluoride titanium, (1-isobutyl group-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) zirconium difluoride, (1-isobutyl group-4, 5,6,7-tetrahydro indenyl) (1-methylindenyl) bifluoride hafnium, (1-isobutyl group-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) two Titanium bromide, (1-isobutyl group-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) dibrominated zirconium, (1-isobutyl group-4,5,6,7-tetrahydrochysene Indenyl) (1-methylindenyl) dibrominated hafnium, (1-isobutyl group-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) diiodinating titanium, (1- Isobutyl group-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) diiodinating zirconium, (1-isobutyl group-4,5,6,7-tetrahydro indenyl) (1- Methylindenyl) diiodinating hafnium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-isobutyl group indenyl) titanium chloride, (1-methyl-4, 5,6,7-tetrahydro indenyl) (1-isobutyl group indenyl) zirconium dichloride, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-isobutyl group indenyl) Hafnium dichloride, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-isobutyl group indenyl) bifluoride titanium, (1-methyl-4,5,6,7-tetrahydrochysene Indenyl) (1-isobutyl group indenyl) zirconium difluoride, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-isobutyl group indenyl) bifluoride hafnium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-isobutyl group indenyl) dibrominated titanium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1- Isobutyl group indenyl) dibrominated zirconium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-isobutyl group indenyl) dibrominated hafnium, (1-methyl- 4,5,6,7-tetrahydro indenyl) (1-isobutyl group indenyl) diiodinating titanium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-isobutyl group indenes Base) diiodinating zirconium, (1-methyl-4,5,6,7-tetrahydro indenyl) (1-isobutyl group indenyl) diiodinating hafnium, (2-isobutyl group-4,5,6, 7-tetrahydro indenyl) (1-methylindenyl) titanium chloride, (2-isobutyl group-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) dichloride Zirconium, (2-isobutyl group-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) hafnium dichloride, (2-isobutyl group-4,5,6,7-tetrahydroindene Base) (1-methylindenyl) bifluoride titanium, (2-isobutyl group-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) zirconium difluoride, (2-is different Butyl-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) bifluoride hafnium, (2-isobutyl group-4,5,6,7-tetrahydro indenyl) (1-methyl Indenyl) dibrominated titanium, (2-isobutyl group-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) dibrominated zirconium, (2-isobutyl group-4,5, 6,7-tetrahydro indenyl) (1-methylindenyl) dibrominated hafnium, (2-isobutyl group-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) diiodo- Change titanium, (2-isobutyl group-4,5,6,7-tetrahydro indenyl) (1-methylindenyl) diiodinating zirconium, (2-isobutyl group-4,5,6,7-tetrahydroindene Base) (1-methylindenyl) diiodinating hafnium, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-isobutyl group indenyl) titanium chloride, (1-first Base-4,5,6,7-tetrahydro indenyl) (2-isobutyl group indenyl) zirconium dichloride, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-isobutyl group Indenyl) hafnium dichloride, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-isobutyl group indenyl) bifluoride titanium, (1-methyl-4,5,6, 7-tetrahydro indenyl) (2-isobutyl group indenyl) zirconium difluoride, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-isobutyl group indenyl) difluoro Change hafnium, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-isobutyl group indenyl) dibrominated titanium, (1-methyl-4,5,6,7-tetrahydroindene Base) (2-isobutyl group indenyl) dibrominated zirconium, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-isobutyl group indenyl) dibrominated hafnium, (1- Methyl-4,5,6,7-tetrahydro indenyl) (2-isobutyl group indenyl) diiodinating titanium, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-isobutyl Base indenyl) diiodinating zirconium, (1-methyl-4,5,6,7-tetrahydro indenyl) (2-isobutyl group indenyl) diiodinating hafnium, (4,5,6,7-tetrahydrochysene Indenyl) (1-phenyl indenyl) titanium chloride, (4,5,6,7-tetrahydro indenyl) (1-phenyl indenyl) zirconium dichloride, (4,5,6,7-tetra- Hydrogen indenyl) (1-phenyl indenyl) hafnium dichloride, (4,5,6,7-tetrahydro indenyl) (1-phenyl indenyl) bifluoride titanium, (4,5,6,7- Tetrahydro indenyl) (1-phenyl indenyl) zirconium difluoride, (4,5,6,7-tetrahydro indenyl) (1-phenyl indenyl) bifluoride hafnium, (4,5,6, 7-tetrahydro indenyl) (1-phenyl indenyl) dibrominated titanium, (4,5,6,7-tetrahydro indenyl) (1-phenyl indenyl) dibrominated zirconium, (4,5, 6,7-tetrahydro indenyl) (1-phenyl indenyl) dibrominated hafnium, (4,5,6,7-tetrahydro indenyl) (1-phenyl indenyl) diiodinating titanium, (4, 5,6,7-tetrahydro indenyl) (1-phenyl indenyl) diiodinating zirconium, (4,5,6,7-tetrahydro indenyl) (1-phenyl indenyl) diiodinating hafnium, (4,5,6,7-tetrahydro indenyl) (2-phenyl indenyl) titanium chloride, (4,5,6,7-tetrahydro indenyl) (2-phenyl indenyl) dichloride Zirconium, (4,5,6,7-tetrahydro indenyl) (2-phenyl indenyl) hafnium dichloride, (4,5,6,7-tetrahydro indenyl) (2-phenyl indenyl) difluoro Change titanium, (4,5,6,7-tetrahydro indenyl) (2-phenyl indenyl) zirconium difluoride, (4,5,6,7-tetrahydro indenyl) (2-phenyl indenyl) two Hafnium fluoride, (4,5,6,7-tetrahydro indenyl) (2-phenyl indenyl) dibrominated titanium, (4,5,6,7-tetrahydro indenyl) (2-phenyl indenyl) Dibrominated zirconium, (4,5,6,7-tetrahydro indenyl) (2-phenyl indenyl) dibrominated hafnium, (4,5,6,7-tetrahydro indenyl) (2-phenylindan Base) diiodinating titanium, (4,5,6,7-tetrahydro indenyl) (2-phenyl indenyl) diiodinating zirconium, (4,5,6,7-tetrahydro indenyl) (2-phenyl Indenyl) diiodinating hafnium, (4,5,6,7-tetrahydro indenyl) (1-benzyl indenyl) titanium chloride, (4,5,6,7-tetrahydro indenyl) (1-benzyl Base indenyl) zirconium dichloride, (4,5,6,7-tetrahydro indenyl) (1-benzyl indenyl) hafnium dichloride, (4,5,6,7-tetrahydro indenyl) (1- Benzyl indenyl) bifluoride titanium, (4,5,6,7-tetrahydro indenyl) (1-benzyl indenyl) zirconium difluoride, (4,5,6,7-tetrahydro indenyl) (1-benzyl indenyl) bifluoride hafnium, (4,5,6,7-tetrahydro indenyl) (1-benzyl indenyl) dibrominated titanium, (4,5,6,7-tetrahydroindene Base) (1-benzyl indenyl) dibrominated zirconium, (4,5,6,7-tetrahydro indenyl) (1-benzyl indenyl) dibrominated hafnium, (4,5,6,7-tetrahydrochysene Indenyl) (1-benzyl indenyl) diiodinating titanium, (4,5,6,7-tetrahydro indenyl) (1-benzyl indenyl) diiodinating zirconium, (4,5,6,7-tetra- Hydrogen indenyl) (1-benzyl indenyl) diiodinating hafnium, (4,5,6,7-tetrahydro indenyl) (2-benzyl indenyl) titanium chloride, (4,5,6,7- Tetrahydro indenyl) (2-benzyl indenyl) zirconium dichloride, (4,5,6,7-tetrahydro indenyl) (2-benzyl indenyl) hafnium dichloride, (4,5,6, 7-tetrahydro indenyl) (2-benzyl indenyl) bifluoride titanium, (4,5,6,7-tetrahydro indenyl) (2-benzyl indenyl) zirconium difluoride, (4,5, 6,7-tetrahydro indenyl) (2-benzyl indenyl) bifluoride hafnium, (4,5,6,7-tetrahydro indenyl) (2-benzyl indenyl) dibrominated titanium, (4, 5,6,7-tetrahydro indenyl) (2-benzyl indenyl) dibrominated zirconium, (4,5,6,7-tetrahydro indenyl) (2-benzyl indenyl) dibrominated hafnium, (4,5,6,7-tetrahydro indenyl) (2-benzyl indenyl) diiodinating titanium, (4,5,6,7-tetrahydro indenyl) (2-benzyl indenyl) are diiodinating Zirconium, (4,5,6,7-tetrahydro indenyl) (2-benzyl indenyl) diiodinating hafnium, (4,5,6,7-tetrahydro indenyl) (cyclopentadienyl group) dichloro Change titanium, (4,5,6,7-tetrahydro indenyl) (cyclopentadienyl group) zirconium dichloride, (4,5,6,7-tetrahydro indenyl) (cyclopentadienyl group) two Hafnium chloride, (4,5,6,7-tetrahydro indenyl) (cyclopentadienyl group) bifluoride titanium, (4,5,6,7-tetrahydro indenyl) (cyclopentadienyl group) Zirconium difluoride, (4,5,6,7-tetrahydro indenyl) (cyclopentadienyl group) bifluoride hafnium, (4,5,6,7-tetrahydro indenyl) (cyclopentadiene Base) dibrominated titanium, (4,5,6,7-tetrahydro indenyl) (cyclopentadienyl group) dibrominated zirconium, (4,5,6,7-tetrahydro indenyl) (ring penta 2 Thiazolinyl) dibrominated hafnium, (4,5,6,7-tetrahydro indenyl) (cyclopentadienyl group) diiodinating titanium, (4,5,6,7-tetrahydro indenyl) (ring penta Dialkylene) diiodinating zirconium, (4,5,6,7-tetrahydro indenyl) (cyclopentadienyl group) diiodinating hafnium, (4,5,6,7-tetrahydro indenyl) (first Cyclopentadienyl group) titanium chloride, (4,5,6,7-tetrahydro indenyl) (methyl cyclopentadienyl) zirconium dichloride, (4,5,6,7-tetra- Hydrogen indenyl) (methyl cyclopentadienyl) hafnium dichloride, (4,5,6,7-tetrahydro indenyl) (methyl cyclopentadienyl) bifluoride titanium, (4,5,6,7-tetrahydro indenyl) (methyl cyclopentadienyl) zirconium difluoride, (4,5,6,7-tetrahydro indenyl) (methyl cyclopentadienyl) Bifluoride hafnium, (4,5,6,7-tetrahydro indenyl) (methyl cyclopentadienyl) dibrominated titanium, (4,5,6,7-tetrahydro indenyl) (methyl ring Pentadienyl) dibrominated zirconium, (4,5,6,7-tetrahydro indenyl) (methyl cyclopentadienyl) dibrominated hafnium, (4,5,6,7-tetrahydroindene Base) (methyl cyclopentadienyl) diiodinating titanium, (4,5,6,7-tetrahydro indenyl) (methyl cyclopentadienyl) diiodinating zirconium, (4,5, 6,7-tetrahydro indenyl) (methyl cyclopentadienyl) diiodinating hafnium, (4,5,6,7-tetrahydro indenyl) (ethyicydopentadi etanyf group) dichloro Change zirconium, (4,5,6,7-tetrahydro indenyl) (ethyicydopentadi etanyf group) hafnium dichloride, (4,5,6,7-tetrahydro indenyl) (ethyl ring penta 2 Thiazolinyl) bifluoride titanium, (4,5,6,7-tetrahydro indenyl) (ethyicydopentadi etanyf group) zirconium difluoride, (4,5,6,7-tetrahydro indenyl) (ethyicydopentadi etanyf group) bifluoride hafnium, (4,5,6,7-tetrahydro indenyl) (ethyicydopentadi etanyf group) dibrominated titanium, (4,5,6,7- Tetrahydro indenyl) (ethyicydopentadi etanyf group) dibrominated zirconium, (4,5,6,7-tetrahydro indenyl) (ethyicydopentadi etanyf group) dibrominated hafnium, (4,5,6,7-tetrahydro indenyl) (ethyicydopentadi etanyf group) diiodinating titanium, (4,5,6,7-tetrahydro indenyl) (ethyicydopentadi etanyf group) Diiodinating zirconium, (4,5,6,7-tetrahydro indenyl) (ethyicydopentadi etanyf group) diiodinating hafnium, (4,5,6,7-tetrahydro indenyl) (propyl group ring Pentadienyl) zirconium dichloride, (4,5,6,7-tetrahydro indenyl) (propyl-cyclopentadienyl) hafnium dichloride, (4,5,6,7-tetrahydroindene Base) (propyl-cyclopentadienyl) bifluoride titanium, (4,5,6,7-tetrahydro indenyl) (propyl-cyclopentadienyl) zirconium difluoride, (4,5, 6,7-tetrahydro indenyl) (propyl-cyclopentadienyl) bifluoride hafnium, (4,5,6,7-tetrahydro indenyl) (propyl-cyclopentadienyl) dibromo Change titanium, (4,5,6,7-tetrahydro indenyl) (propyl-cyclopentadienyl) dibrominated zirconium, (4,5,6,7-tetrahydro indenyl) (propyl group ring penta 2 Thiazolinyl) dibrominated hafnium, (4,5,6,7-tetrahydro indenyl) (propyl-cyclopentadienyl) diiodinating titanium, (4,5,6,7-tetrahydro indenyl) (propyl-cyclopentadienyl) diiodinating zirconium, (4,5,6,7-tetrahydro indenyl) (propyl-cyclopentadienyl) diiodinating hafnium, (4,5,6,7- Tetrahydro indenyl) (n-butyl cyclopentadienyl) zirconium dichloride, (4,5,6,7-tetrahydro indenyl) (n-butyl cyclopentadienyl) dichloro Change hafnium, (4,5,6,7-tetrahydro indenyl) (n-butyl cyclopentadienyl) bifluoride titanium, (4,5,6,7-tetrahydro indenyl) (normal-butyl Cyclopentadienyl group) zirconium difluoride, (4,5,6,7-tetrahydro indenyl) (n-butyl cyclopentadienyl) bifluoride hafnium, (4,5,6,7-tetra- Hydrogen indenyl) (n-butyl cyclopentadienyl) dibrominated titanium, (4,5,6,7-tetrahydro indenyl) (n-butyl cyclopentadienyl) dibrominated Zirconium, (4,5,6,7-tetrahydro indenyl) (n-butyl cyclopentadienyl) dibrominated hafnium, (4,5,6,7-tetrahydro indenyl) (normal-butyl ring penta Dialkylene) diiodinating titanium, (4,5,6,7-tetrahydro indenyl) (n-butyl cyclopentadienyl) diiodinating zirconium, (4,5,6,7-tetrahydroindene Base) (n-butyl cyclopentadienyl) diiodinating hafnium, (4,5,6,7-tetrahydro indenyl) (isobutylcyclopentadienyl) zirconium dichloride, (4,5,6,7-tetrahydro indenyl) (isobutylcyclopentadienyl) hafnium dichloride, (4,5,6,7-tetrahydro indenyl) (isobutyl basic ring penta 2 Thiazolinyl) bifluoride titanium, (4,5,6,7-tetrahydro indenyl) (isobutylcyclopentadienyl) zirconium difluoride, (4,5,6,7-tetrahydro indenyl) (isobutylcyclopentadienyl) bifluoride hafnium, (4,5,6,7-tetrahydro indenyl) (isobutylcyclopentadienyl) dibrominated titanium, (4,5, 6,7-tetrahydro indenyl) (isobutylcyclopentadienyl) dibrominated zirconium, (4,5,6,7-tetrahydro indenyl) (isobutylcyclopentadienyl) Dibrominated hafnium, (4,5,6,7-tetrahydro indenyl) (isobutylcyclopentadienyl) diiodinating titanium, (4,5,6,7-tetrahydro indenyl) (isobutyl Cyclopentadienyl group) diiodinating zirconium, (4,5,6,7-tetrahydro indenyl) (isobutylcyclopentadienyl) diiodinating hafnium, (4,5,6,7- Tetrahydro indenyl) (1-methyl-3-n-butyl cyclopentadienyl) zirconium dichloride, (4,5,6,7-tetrahydro indenyl) (positive fourth of 1-methyl-3- Cyclopentadienyl group) hafnium dichloride, (4,5,6,7-tetrahydro indenyl) (1-methyl-3-n-butyl cyclopentadienyl) bifluoride titanium, (4,5,6,7-tetrahydro indenyl) (1-methyl-3-n-butyl cyclopentadienyl) zirconium difluoride, (4,5,6,7-tetrahydro indenyl) (1-first Base-3-n-butyl cyclopentadienyl) bifluoride hafnium, (4,5,6,7-tetrahydro indenyl) (1-methyl-3-n-butyl cyclopentadienyl) Dibrominated titanium, (4,5,6,7-tetrahydro indenyl) (1-methyl-3-n-butyl cyclopentadienyl) dibrominated zirconium, (4,5,6,7-tetrahydrochysene Indenyl) (1-methyl-3-n-butyl cyclopentadienyl) dibrominated hafnium, (4,5,6,7-tetrahydro indenyl) (1-methyl-3-normal-butyl ring Pentadienyl) diiodinating titanium, (4,5,6,7-tetrahydro indenyl) (1-methyl-3-n-butyl cyclopentadienyl) diiodinating zirconium, (4,5, 6,7-tetrahydro indenyl) (1-methyl-3-n-butyl cyclopentadienyl) diiodinating hafnium, (4,5,6,7-tetrahydro indenyl) (pentamethyl ring Pentadienyl) zirconium dichloride, (4,5,6,7-tetrahydro indenyl) (pentamethylcyclopentadiene base) hafnium dichloride, (4,5,6,7-tetrahydrochysene Indenyl) (pentamethylcyclopentadiene base) bifluoride titanium, (4,5,6,7-tetrahydro indenyl) (pentamethylcyclopentadiene base) zirconium difluoride, (4,5,6,7-tetrahydro indenyl) (pentamethylcyclopentadiene base) bifluoride hafnium, (4,5,6,7-tetrahydro indenyl) (pentamethyl ring penta 2 Thiazolinyl) dibrominated titanium, (4,5,6,7-tetrahydro indenyl) (pentamethylcyclopentadiene base) dibrominated zirconium, (4,5,6,7-tetrahydro indenyl) (pentamethylcyclopentadiene base) dibrominated hafnium, (4,5,6,7-tetrahydro indenyl) (pentamethylcyclopentadiene base) diiodinating titanium, (4, 5,6,7-tetrahydro indenyl) (pentamethylcyclopentadiene base) diiodinating zirconium, (4,5,6,7-tetrahydro indenyl) (pentamethylcyclopentadiene Base) diiodinating hafnium, (4,5,6,7-tetrahydro indenyl) (tetramethyl-ring pentadienyl) zirconium dichloride, (4,5,6,7-tetrahydro indenyl) (tetramethyl-ring pentadienyl) hafnium dichloride, (4,5,6,7-tetrahydro indenyl) (tetramethyl-ring pentadienyl) bifluoride titanium, (4,5, 6,7-tetrahydro indenyl) (tetramethyl-ring pentadienyl) zirconium difluoride, (4,5,6,7-tetrahydro indenyl) (tetramethyl-ring pentadienyl) Bifluoride hafnium, (4,5,6,7-tetrahydro indenyl) (tetramethyl-ring pentadienyl) dibrominated titanium, (4,5,6,7-tetrahydro indenyl) (tetramethyl Cyclopentadienyl group) dibrominated zirconium, (4,5,6,7-tetrahydro indenyl) (tetramethyl-ring pentadienyl) dibrominated hafnium, (4,5,6,7- Tetrahydro indenyl) (tetramethyl-ring pentadienyl) diiodinating titanium, (4,5,6,7-tetrahydro indenyl) (tetramethyl-ring pentadienyl) diiodo- Change zirconium, (4,5,6,7-tetrahydro indenyl) (tetramethyl-ring pentadienyl) diiodinating hafnium, (4,5,6,7-tetrahydro indenyl) (cyclopenta ring Pentadienyl) zirconium dichloride, (4,5,6,7-tetrahydro indenyl) (cyclopenta cyclopentadienyl group) hafnium dichloride, (4,5,6,7-tetrahydrochysene Indenyl) (cyclopenta cyclopentadienyl group) bifluoride titanium, (4,5,6,7-tetrahydro indenyl) (cyclopenta cyclopentadienyl group) zirconium difluoride, (4,5,6,7-tetrahydro indenyl) (cyclopenta cyclopentadienyl group) bifluoride hafnium, (4,5,6,7-tetrahydro indenyl) (cyclopenta ring penta 2 Thiazolinyl) dibrominated titanium, (4,5,6,7-tetrahydro indenyl) (cyclopenta cyclopentadienyl group) dibrominated zirconium, (4,5,6,7-tetrahydro indenyl) (cyclopenta cyclopentadienyl group) dibrominated hafnium, (4,5,6,7-tetrahydro indenyl) (cyclopenta cyclopentadienyl group) diiodinating titanium, (4,5, 6,7-tetrahydro indenyl) (cyclopenta cyclopentadienyl group) diiodinating zirconium, (4,5,6,7-tetrahydro indenyl) (cyclopenta cyclopentadienyl group) Diiodinating hafnium, (4,5,6,7-tetrahydro indenyl) (cyclohexyl ring pentadienyl) zirconium dichloride, (4,5,6,7-tetrahydro indenyl) (hexamethylene Cyclopentadienyl group) hafnium dichloride, (4,5,6,7-tetrahydro indenyl) (cyclohexyl ring pentadienyl) bifluoride titanium, (4,5,6,7- Tetrahydro indenyl) (cyclohexyl ring pentadienyl) zirconium difluoride, (4,5,6,7-tetrahydro indenyl) (cyclohexyl ring pentadienyl) difluoro Change hafnium, (4,5,6,7-tetrahydro indenyl) (cyclohexyl ring pentadienyl) dibrominated titanium, (4,5,6,7-tetrahydro indenyl) (cyclohexyl ring Pentadienyl) dibrominated zirconium, (4,5,6,7-tetrahydro indenyl) (cyclohexyl ring pentadienyl) dibrominated hafnium, (4,5,6,7-tetrahydrochysene Indenyl) (cyclohexyl ring pentadienyl) diiodinating titanium, (4,5,6,7-tetrahydro indenyl) (cyclohexyl ring pentadienyl) diiodinating zirconium, (4,5,6,7-tetrahydro indenyl) (cyclohexyl ring pentadienyl) diiodinating hafnium, (4,5,6,7-tetrahydro indenyl) (sila cyclobutyl ring Pentadienyl) zirconium dichloride, (4,5,6,7-tetrahydro indenyl) (sila cyclobutyl cyclopentadienyl group) hafnium dichloride, (4,5,6,7- Tetrahydro indenyl) (sila cyclobutyl cyclopentadienyl group) bifluoride titanium, (4,5,6,7-tetrahydro indenyl) (sila cyclobutyl ring penta 2 Thiazolinyl) zirconium difluoride, (4,5,6,7-tetrahydro indenyl) (sila cyclobutyl cyclopentadienyl group) bifluoride hafnium, (4,5,6,7-tetrahydrochysene Indenyl) (sila cyclobutyl cyclopentadienyl group) dibrominated titanium, (4,5,6,7-tetrahydro indenyl) (sila cyclobutyl cyclopentadienyl group) Dibrominated zirconium, (4,5,6,7-tetrahydro indenyl) (sila cyclobutyl cyclopentadienyl group) dibrominated hafnium, (4,5,6,7-tetrahydro indenyl) (sila cyclobutyl cyclopentadienyl group) diiodinating titanium, (4,5,6,7-tetrahydro indenyl) (sila cyclobutyl cyclopentadienyl group) are diiodinating Zirconium, (4,5,6,7-tetrahydro indenyl) (sila cyclobutyl cyclopentadienyl group) diiodinating hafnium, its mixture and similar compound thereof.

The metallocene compound of the present invention is not limited to above-named example, but includes comprising and have other and replace or do not take The metallocene compound of the part of tetrahydro indenyl (4HInd) core in generation.Can be by the routine side for preparing metallocene compound Method prepares the metallocene compound of the present invention.Such as, as shown in examples detailed above, double (tetrahydro indenyl) zirconium dichlorides and zirconium chloride are anti- Should be to obtain (tetrahydro indenyl) tri-chlorination zirconium, and (tetrahydro indenyl) tri-chlorination zirconium of obtaining and the reaction of indenyl lithium are to obtain (four Hydrogen indenyl) (indenyl) zirconium dichloride.

The olefin Polymerization catalyst compositions (system) of the present invention includes metallocene compound and activator, described activator Can react with metallocene compound so that metallocene compound has catalytic activation effect.As activator, it is possible to be used alone Conventional activating agent, such as, alkylaluminoxane, organo-aluminum compound, large volume (bulky) fluoro-aromatic compounds compound, modification Clay, lewis acid inorganic oxide etc., or their mixture can be used.The alkylaluminoxane represented as formula 2, The straight chain being purchased, the ring-type or alkylaluminoxane of network structure can be used.The limiting examples of alkylaluminoxane includes leading to The alkyl aikyiaiurnirsoxan beta that formula 3 and 4 represents, it is the oligomer with straight chain or circulus, such as MAO, ethyl alumina Alkane, butyla-luminoxane, isobutyl aluminium alkoxide, hexyl aikyiaiurnirsoxan beta, octyl alumoxane, decyl aikyiaiurnirsoxan beta, its mixture etc., and excellent Electing the aromatic hydrocarbon solution of aikyiaiurnirsoxan beta as, it is the hydrocarbon solution of aikyiaiurnirsoxan beta of business, and is more preferably dissolved in the aluminum in toluene Oxygen alkane.In the present invention, it is possible to use the mixture of the aikyiaiurnirsoxan beta of single aikyiaiurnirsoxan beta or more than one.

[formula 2]

In formula 2, R ' is the hydrocarbyl group of 1 to 10 carbon atom, and x is the integer of 1 to 70.

[formula 3]

[formula 4]

In formula 3 and 4, R ' independently be hydrocarbyl group, the straight or branched alkyl base of preferably 1 to 10 carbon atom Group.That is, R ' can be same to each other or different to each other.It is highly preferred that the major part of R ' is methyl.X is 1 to 50, preferably 1 to 40 whole Number.Y is 3 to 50, the integer of preferably 10 to 40.Alkylaluminoxane can be prepared, such as to trialkyl by multiple conventional method Aluminum adds appropriate water, or makes the hydrocarbon compound comprising water or inorganic hydrated salt react with trialkylaluminium, thus, generally obtains straight Chain aikyiaiurnirsoxan beta and the mixture of Cyclic aluminoxane.

Additionally, the carbon monoxide-olefin polymeric of the present invention can comprise the organo-aluminium chemical combination that the formula 5 as Impurity removal agent represents Thing.

[formula 5]

In formula 5, R²、R³And R⁴Independently 1 to the alkyl of 10 carbon atoms or alkoxyl or halide group (fluorin radical, cl radical, bromine group, iodine group etc.), and R²、R³And R⁴In at least one be alkyl.Organo-aluminum compound Limiting examples includes: trialkylaluminium, such as, trimethyl aluminium, triethyl aluminum, tri-butyl aluminum, three hexyl aluminum, trioctylaluminum, Tridecyl aluminum etc.；Dialkyl group aluminum alkoxide, such as dimethyl aluminum methoxide, diethyl aluminum methoxide, dibutyl aluminum methoxide etc.； Dialkylaluminum halides, such as, dimethylaluminum chloride, diethyl aluminum chloride, dibutyl aluminum chloride etc.；Alkyl dialkoxy aluminum, example As, methyl dimethoxy epoxide aluminum, ethyl dimethoxy aluminum, butyl dimethoxy aluminum etc.；Alkyl dihalides aluminum, such as, methyl dichloro Change aluminum, ethylaluminum dichloride, buty laluminum dichloride etc.；And mixture.

In the carbon monoxide-olefin polymeric of the present invention, the having by the substituted fragrance of fluorine of activator can be denoted as by formula 6 The bulky compounds (large volume fluoro-aromatic compounds compound) of base.

[formula 6]

[C][D]

In formula 6, C is cation, and it is the lewis base of binding hydrogen ions, or has the metal of oxidability or non- Metallic compound, and D is the compound including the periodic table of elements the 5th race to the element and organic substance of the 15th race.Greatly The limiting examples of volume fluoro-aromatic compounds compound (by the ionic compound of fluorine substituted fragrance boron) includes four (five fluorine Phenyl) boric acid trimethyl ammonium, four (pentafluorophenyl group) boric acid triethyl ammonium, four (pentafluorophenyl group) boric acid tripropyl ammonium, four (phenyl-pentafluorides Base) boric acid tributyl ammonium, four (pentafluorophenyl group) boric acid aniline, four (pentafluorophenyl group) pyridine borate, four (pentafluorophenyl group) boric acid two Cyclopentadienyl ferrum, four (pentafluorophenyl group) boric acid silver, three (pentafluorophenyl group) borine, three (3,4,5-trifluorophenyl) borine, its mixture etc..

The limiting examples of the modified clay that can serve as activator includes N, accelerine montmorillonite, N, N-diformazan Base aniline hectorite, its mixture etc..Additionally, the example as the lewis acid inorganic oxide of activator includes being fluorinated sial Deng.

The metallocene compound that can be represented by mixing formula 1 and aikyiaiurnirsoxan beta prepare the olefin polymerization catalysis of the present invention Compositions.Wherein, the metallocene compound that the formula 1 relative to 1 mole represents, aluminum in the aikyiaiurnirsoxan beta of the expressions such as formula 2,3,4 Amount be 1 mole to 100,000 mole, preferably 5 moles to 5,000 mole.When large volume fluoro-aromatic compounds compound is (logical Formula 6) when being organoboron compound, mol ratio ([organoboron compound]/[the cyclopentadienyl gold of organoboron compound and metallocene compound Belong to compound]) usually 1 to 1,000, and preferably 1 to 100.If by metallocene compound and the organo-aluminium of the present invention Compound, the modified mixing such as clay, lewis acid inorganic compound, then mixing ratio can be according to application target, catalyst type Deng and change, and suitably can set according to routine techniques.

The compound of energy mixed catalyst composition, and the most specifically limit.Such as, metallocene formula 1 represented Compound and aikyiaiurnirsoxan beta mix 5 minutes to 10 hours, preferably 15 minutes to 4 hours.The mixed process of compound is unrestricted, but It is desirably, it should there is no solvent or the unreactive hydrocarbons solvent at such as heptane, hexane, benzene,toluene,xylene or its mixture In the presence of, under the inert environments of nitrogen or argon, by two kinds of compound mixing.The temperature of mixed process is 0 ° C to 150 ° C, preferably 10 ° C to 90 ° of C.Catalyst solution during wherein catalyst solves homogeneously in hydrocarbon solvent can be made by its status praesens With, or after having removed solvent, it is possible to use the catalyst of pressed powder state.Can be by carrying out catalyst solution Precipitation, and from reaction, solidify precipitate, prepare the catalyst of pressed powder state.

Present invention also offers olefin Polymerization catalyst compositions, comprise the metallocene compound of formula 1 expression with logical After the carbon monoxide-olefin polymeric of the activator of the such as aikyiaiurnirsoxan beta that formula 2 represents contacts with organic or inorganic carrier, prepare described alkene Polymerized hydrocarbon carbon monoxide-olefin polymeric.Carbon monoxide-olefin polymeric and/or activator can be with carrier loaded form or insoluble with carrier The form of granule and the form of homogeneous solution and exist.Elaboration is used for making the carbon monoxide-olefin polymeric of the present invention contact with carrier Method.First, the aluminium alkoxide compound that the metallocene compound represented by mixing formula 1 and formula 2 are represented is prepared molten The catalyst of liquid status；And (such as, hole dimension is with porous carrier to make catalystExtremelyAnd pore volume is 0.1cm³/ g to 5.0cm³The silica supports of/g) contact to form slurry.It follows that under 0 ° of C to 120 ° of C, use frequency Sound wave or the wave of oscillation for 1kHz to 10.000kHz process mixture, and the time is 1 hour to 6 hours, so that catalytic component Penetrate into equably in the hole of carrier.Then, dry catalyst slurry is flowed down to form pressed powder state in vacuum or nitrogen Catalyst.Sound wave or the wave of oscillation are preferably ultrasound wave, and more preferably frequency is the ripple of 20kHz to 500kHz.To catalysis After agent applies sound wave or the wave of oscillation, the step making catalyst be carried on carrier can also include using urging of hydrocarbon wash load The step of agent, described hydrocarbon is selected from pentane, hexane, heptane, different paraffin, toluene, dimethylbenzene and mixture thereof.

As carrier, it is possible to use and there is micropore and the porous inorganic compounds of high surface area, inorganic salt and organic compound Thing, and unrestricted.If shape can be kept, then for the shape of inorganic carrier in the preparation process of the catalyst of load Have no particular limits, and can be any shape, such as powder, granule, sheet, paper tinsel, fiber etc..Shape regardless of inorganic carrier Shape, but the greatest length of inorganic carrier is usually 5 μm to 200 μm, preferably 10 μm to 100 μm, the preferred surface of inorganic carrier Amass as 50m²/ g to 1,000m²/ g, and preferably pore volume is 0.05cm³/ g to 5cm³/g.Generally, should process before use Inorganic carrier is to remove water or hydroxyl from which.Can be by under the inert environments of such as air, nitrogen, argon etc., at 200 ° of C To 900 ° of C, calcinated support carries out described process.The limiting examples of inorganic salt carrier or inorganic carrier includes titanium dioxide Silicon, aluminium oxide, Alumina, zeolite, magnesium chloride (MgCl₂), calcium chloride (CaCl₂), magnesium oxide (MgO), zirconium dioxide (ZrO₂), two Titanium oxide (TiO₂), diboron trioxide (B₂O₃), calcium oxide (CaO), zinc oxide (ZnO), Barium monoxide (BaO), thorium oxide (ThO₂) And mixture, such as silica-magnesia (SiO₂-MgO), silica-alumina (SiO₂-Al₂O₃), silicon dioxide- Titanium dioxide (SiO₂-TiO₂), silicon dioxide-vanadic anhydride (SiO₂-V₂O₅), silicon dioxide-chromic acid (SiO₂- CrO₃), silica-titania-magnesium oxide (SiO₂-TiO₂-MgO) etc..A small amount of carbonic acid can be added to these compounds Salt, sulfate or nitrate.The limiting examples of organic carrier includes the polymer etc. of starch, cyclodextrin, synthesis.

The example that can be used for the solvent that the catalyst making the present invention contacts with carrier includes: aliphatic hydrocarbon solvent, such as, and penta Alkane, hexane, heptane, octane, nonane, decane, hendecane, dodecane etc.；Aromatic hydrocarbon solvents, such as benzene, monochloro-benzene, dichloro Benzene, trichloro-benzenes, toluene etc.；Halogenated aliphatic hydrocarbon solvent, such as dichloromethane, chloroform, dichloroethanes, trichloroethane etc.； Deng.Solvent and mixture thereof can be used for loading process.Metallocene in the olefin Polymerization catalyst compositions contacted with carrier The ratio of compound and aikyiaiurnirsoxan beta is not particularly limited, but desirably, the metallocene chemical combination that the formula 1 relative to 1 mole represents Thing, in the aikyiaiurnirsoxan beta that formula 2 represents the amount of aluminum be 1 mole to 1,000 mole, preferably 1 mole to 500 moles.

The invention provides olefine polymerizing process, it is included in the presence of polymerization catalyst composition and is polymerized at least one The step of alkene, described polymerization catalyst composition comprises the metallocene compound that formula 1 represents, if desired, comprise formula 2 table The activator of the such as aluminium alkoxide compound shown, organic or inorganic carrier etc..The olefin Polymerization catalyst compositions energy of the present invention With the form loaded by inorganic carrier (silicon dioxide, aluminium oxide, silica-alumina mixture etc.) or insoluble with carrier The property form of granule and the form of homogeneous solution and exist.Accordingly, it is capable to it is anti-in solution phase, slurry phase, body phase or gas-phase polymerization The olefine polymerizing process of the present invention is implemented in should.The condition of each polyreaction can be (homogeneous or heterogeneous according to catalyst condition (phase of load)), polymerization (polymerisation in solution, slurry polymerization, gas-phase polymerization), target polymer performance or polymer form and Change.When solution phase or slurry mutually in be polymerized time, solvent or alkene itself can serve as reaction medium.The example of solvent Including propane, butane, pentane, hexane, octane, decane, dodecane, Pentamethylene., methyl cyclopentane, hexamethylene, benzene, toluene, two Toluene, dichloromethane, ethyl chloride, 1,2-dichloroethanes, chlorobenzene etc., and if desired, the solvent of a certain ratio can be used to mix Thing.

The alkene used in polymerization can be single alkene or the mixture of two or more alkene.That is, can be by The olefin Polymerization catalyst compositions of the present invention is used for copolymerization and the homopolymerization of monomer of monomers/comonomers.For polymerization or The preferred embodiment of the alkene of copolymerization includes alpha-olefin, cycloolefin, diene, triolefin, styrene etc..Alpha-olefin include 2 to 12, excellent Select the aliphatic alkene of 2 to 8 carbon atoms, more specifically ethylene, propylene, butene-1, amylene-1,3-methyl butene-1, oneself Alkene-1,4-methylpentene-1,3-methylpentene-1, heptene-1, octene-1, decylene-1,4,4-dimethyl-1-amylene, 4,4-bis- Ethyl-1-hexene, 3,4-dimethyl-1-hexene etc..Alpha-olefine polymerizing can be made to form homopolymer, alternate copolymer, random Copolymer or block copolymer.The copolymerization of alpha-olefin includes the alpha-olefin (example of ethylene and 3 to 12, preferably 3 to 8 carbon atoms As, ethylene and propylene, ethylene and butene-1, ethylene and hexene-1, ethylene and 4-methylpentene-1, ethylene and octene-1 etc.) The alpha-olefin of copolymerization and propylene and 4 to 12, preferably 4 to 8 carbon atoms (propylene and butene-1, propylene and 4-methylpentene- 1, propylene and 4-methyl butene-1, propylene and hexene-1, propylene and octene-1) copolymerization.At ethylene or propylene and other α-alkene In the copolymerization of hydrocarbon, relative to total monomer, the amount of other alpha-olefin can be 90 moles of % or lower, and specifically, for often Rule ethylene copolymer, is 40 moles of % or lower, preferably 30 moles % or lower, and more preferably 20 moles % or lower, and And for conventional propylene copolymer, be 1 mole of % to 90 mole of %, preferably 5 moles % to 90 mole of %, and more preferably 10 Mole % to 70 mole of %.

As cycloolefin, to use carbon number be 3 to 24, is preferably the cycloolefin of 3 to 18.The example of cycloolefin includes ring penta Alkene, cyclobutane, cyclohexene, 3-methylcyclohexene, cyclo-octene, tetracyclodecene, eight cyclodecenes, bicyclopentadiene, norborene, 5- Methyl-2-norborene, 5-ethylene-2-norborene, 5-isobutyl group-2-norborene, 5,6-dimethyl-2-norborene, 5,5,6-trimethyl-2-norborene, vinyl norbornene etc..Cycloolefin energy and alpha-olefin copolymer, and relative to copolymer, The amount of cycloolefin is 1 mole of % to 50 mole of %, preferably 2 moles % to 50 mole of %.Preferably diene and triolefin includes having two The polyenoid of 4 to 26 carbon atoms of individual or three double bonds.The instantiation of diene and triolefin includes 1,3-butadiene, 1,4-penta Diene, 1,4-hexadiene, 1,5-hexadiene, 1,9-decadinene, 2-methyl isophthalic acid, 3-butadiene etc..Cinnamic preferred embodiment bag Include styrene or by the alkyl of 1 to 10 carbon atom, alkoxyl or haloalkyl；Halogen group；Amido；Silicyls etc. are substituted Substituted styrene.

In the polymerization of alpha-olefin or copolymerization of the present invention, the amount of the metallocene compound that formula 1 represents is not restricted to certain One scope.But, in polymerization reaction system, the central metal concentration of the metallocene compound of formula 1 is preferably 10^-8mol/l To 10¹Mol/l, and more preferably 10^-7Mol/l to 10^-2mol/l.If the amount of metallocene compound goes beyond the scope, then it is catalyzed The activity of agent is not enough, or may use unnecessary excess catalyst.In the polymerization or copolymerization of the present invention, polymerization temperature energy Change in scope widely according to reactant, reaction condition etc..When carrying out polymerisation in solution, temperature is usually 0 ° C to 250 ° C, and more preferably 10 ° C to 200 ° of C.When carrying out slurry or gas-phase polymerization, temperature is usually 0 ° of C to 120 ° of C, and more It is preferably 20 ° of C to 100 ° of C.Polymerization pressure usually air is depressed into 500kg/cm², and more preferably air is depressed into 50kg/ cm².React with batch type, semicontinuous type or continuous and implement polyreaction.The two or more of differential responses condition can be passed through Step implements polymerization.By changing polymerization temperature, or control by the olefinic polymerization of the present invention by injecting Hydrogen Energy to reactor The molecular weight of final polymer prepared by catalyst.Preferably, the density of the alkene of preparation is 0.91g/cm³To 0.94g/cm³。

The olefin Polymerization catalyst compositions of the present invention can be used not only for the mass polymerization of olefinic monomer, moreover it can be used to alkene The prepolymerization of monomer.In pre-polymerization process, relative to the catalyst of 1g, can be with 0.05g to 500g, preferably 0.1g to 300g, And the amount of more preferably 0.2g to 100g produces olefin polymer or copolymer.The example being suitable to prepolymerized alkene includes 2 To the alpha-olefin of 20 carbon atoms, such as, ethylene, propylene, 1-butylene, 1-amylene, 4-methyl-1-pentene, 1-hexene, 1-are pungent Alkene, 1-decene, 1-laurylene, 1-tetradecylene, 3-methyl-1-butene, 3-Methyl-1-pentene etc..For prepolymerized more suitable Alkene with in mass polymerization use alkene identical.

Hereinafter, it is provided that preferred embodiment is to be more fully understood that the present invention.But, the invention is not restricted to following reality Execute example.In the examples below that, use Schlenk method to prepare olefin polymerization catalysis, stop sky the most completely Gas and moisture, and purification and dry nitrogen are used as noble gas.Under inert nitrogen environment, use and receive metal and be dried molten Agent.Melt index (MI) and the HLM (high capacity melt index) of polymer is measured according to ASTM D1238, and according to ASTM D1505 measures the density of polymer.

[embodiment 1]

A. the preparation of (tetrahydro indenyl) (indenyl) zirconium dichloride

In the 500ml round-bottomed flask of nitrogen environment, double (tetrahydro indenyl) the zirconium dichloride 1.065g (2.66mmol) of interpolation, Zirconium chloride 0.66g (2.83mmol) and toluene 100ml, and react 18 hours under 90 ° of C, stir simultaneously.React it completing After, by filtering product, filtrate is assembled.In 500ml flask, add indenyl lithium 0.66g (5.406mmol), then add Add filtrate, and under 90 ° of C, mixture solution is reacted 18 hours, stir simultaneously.Solvent is removed by vacuum draw.Additionally, After the extraction and filtration of 100ml dichloromethane, again remove solvent.The hexane of 50ml is added to form slurry to product Body, and filter slurry and wash with 500ml hexane, and it is dried in a vacuum to obtain (the tetrahydrochysene of 1.52g (productivity: 72%) Indenyl) (indenyl) zirconium dichloride.1H NMR (500MHz, the CDCl of (tetrahydro indenyl) (indenyl) zirconium dichloride obtained₃) analyze Result is 1.54-1.50 (m, 2, C9H11), 1.79-1.70 (m, 2, C9H11), 2.44-2.38 (m, 2, C9H11), 2.74- 2.68(m,2,C9H11),5.32-5.31(m,2,C9H11),6.05-6.34(m,1,C9H11),6.50-6.46(m,2, C9H7),6.86-6.85(m,1,C9H7),7.24-7.22(m,2,C9H7),7.66-7.64(m,2,C9H7)。

B. the preparation of carbon monoxide-olefin polymeric

In the 500ml flask of nitrogen environment, by (tetrahydro indenyl) (indenyl) zirconium dichloride 92mg and MAO (MAO, Albemarle company, 10% toluene solution) 20ml mixes, and reacts 30 minutes to obtain catalyst solution.To preparation The silicon dioxide of calcining under 220 ° of C of catalyst solution interpolation 4g, and implement the ultrasound wave of 1 hour, and abandon supernatant Liquid.With the solid particle of hexane (once) wash residual, and it is dried in a vacuum to obtain free flowable pressed powder Supported catalyst.

C. the copolymerization of ethylene/hexene-1

Under about 110 ° of C, iso-butane (once) and ethylene (five times) is used to clean the 1 L stainless steel autoclave with chuck Reactor, to remove impurity, is subsequently cooled to 67 ° of C, and described chuck is used for supplying cooling water to control polymerization temperature.To washing Reactor adds iso-butane 400ml and triisobutyl aluminium 1.0mmol, and stirs under 75 ° of C.Also add isobutyl to reactor The supported catalyst 40mg of alkane 100ml and acquisition, then adds ethylene and the 1-hexene of 40ml, until the dividing potential drop of ethylene becomes 130psig.Under 75 ° of C, polymerization is carried out 4 hours, the stagnation pressure of reactor is held in 290psig simultaneously.During being polymerized, The dividing potential drop of ethylene is held in 130psig, and compared with the ethylene additionally added, adds 1-hexene continuously with 10 weight %, Flow by ethylene described in mass flow meter measurement.After completing polymerization, discharge unreacted 1-hexene and iso-butane, and And the free flowable polymer of 395g is obtained from reactor.During 4 hours polyreactions, rate of polymerization is made to keep steady Fixed.The catalysis activity of polymerization is 2,240g polymer/g catalyst hour, and MI (the melted finger of the polymer obtained Number) it is 1.16g/10min, and the density of the polymer obtained is 0.9277g/cm³。

[embodiment 2]

A. the preparation of (tetrahydro indenyl) (2-methylindenyl) zirconium dichloride

In the 500ml round-bottomed flask of nitrogen environment, add double (tetrahydro indenyl) zirconium dichloride 3.184g (8mmol), chlorine Change zirconium 1.873g (8.4mmol) and toluene 150ml, and react 24 hours under 90 ° of C, stir simultaneously.React it completing After, by filtering product, filtrate is assembled.In 500ml flask, add 2-methylindenyl lithium 2.176g (16mmol), so Rear interpolation filtrate, and under 90 ° of C, mixture solution is reacted 24 hours, stir simultaneously.Solvent is removed by vacuum draw. Additionally, after the extraction and filtration of 100ml dichloromethane, again remove solvent.To product add 50ml hexane with Form slurry, and filter slurry and wash with 500ml hexane, and be dried in a vacuum to obtain 3.45g (productivity: 52%) (tetrahydro indenyl) (2-methylindenyl) zirconium dichloride.The 1H NMR of (tetrahydro indenyl) (2-methylindenyl) zirconium dichloride obtained (500MHz,CDCl₃) analysis result is 1.49-1.42 (m, 2, C9H11), 1.75-1.68 (m, 2, C9H11), 2.28 (s, 3, C10H9),2.37-2.33(m,2,C9H11),2.69-2.64(m,2,C9H11),5.09-5.08(m,2,C10H11),5.80- 5.79(m,1,C10H11),6.236(s,2,C10H9),7.13-7.10(m,2,C10H9),7.55-7.53(m,2,C10H9)。

B. the preparation of carbon monoxide-olefin polymeric

In the 500ml flask of nitrogen environment, by (tetrahydro indenyl) (2-methylindenyl) zirconium dichloride 95mg and aluminium methyl Oxygen alkane (MAO, Albemarle company, 10% toluene solution) 20ml mixes, and reacts 30 minutes to obtain catalyst solution.To system The silicon dioxide of calcining under 220 ° of C of standby catalyst solution interpolation 4g, and implement the ultrasound wave of 1 hour, and abandon Supernatant.With the solid particle of hexane (once) wash residual, and it is dried in a vacuum to obtain free flowable solid The supported catalyst of powder.

C. the copolymerization of ethylene/hexene-1

In addition to using the catalyst of the 61mg prepared in above-mentioned steps, gather according to the polymerization of embodiment 1 Close 4 hours with the polymer obtaining 317g.During 4 hours polyreactions, rate of polymerization is made to keep stable.The catalysis of polymerization is lived Property is 1,650g polymer/g catalyst hour, and the MI (melt index) of the polymer obtained is 0.64g/10min, And the density of the polymer obtained is 0.9287g/cm³。

[embodiment 3]

A. the preparation of (tetrahydro indenyl) (1-normal-butyl indenyl) zirconium dichloride

In the 500ml round-bottomed flask of nitrogen environment, double (tetrahydro indenyl) the zirconium dichloride 3.184g (8.0mmol) of interpolation, Zirconium chloride 1.873g (8.4mmol) and toluene 150ml, and react 24 hours under 90 ° of C, stir simultaneously.React it completing After, by filtering product, filtrate is assembled.In 500ml flask, add 1-normal-butyl indenyl lithium 2.85g (16mmol), Then add filtrate, and under 90 ° of C, mixture solution is reacted 24 hours, stir simultaneously.Removed molten by vacuum draw Agent.Additionally, after the extraction and filtration of 100ml dichloromethane, again remove solvent.The hexane of 50ml is added to product To form slurry, and filter slurry and wash with 500ml hexane, and be dried in a vacuum to obtain 3.13g (productivity: 43%) (tetrahydro indenyl) (1-normal-butyl indenyl) zirconium dichloride.(tetrahydro indenyl) (the 1-normal-butyl indenyl) zirconium dichloride obtained 1H NMR (500MHz, CDCl₃) analysis result be 0.89-0.91 (m, 3, C11H12), 1.466-1.493 (reactant, m), 1.68-1.72 (reactant, m), 2.325 (m, 1, C9H11), 2.415 (m, 1, C9H11), 2.584 (m, 1, C9H11), 2.703 (m,1,C9H11),2.97-2.98(m,2,C11H12),4.931(m,2,C9H11), 5.50(m,1,C9H11),6.0(m,1, C11H12),6.328(m,1,C11H12),6.592(m,1,C11H12),7.15-7.19(m,2,C11H12),7.53-7.56 (m,2,C11H12)。

B. the preparation of carbon monoxide-olefin polymeric

In the 500ml flask of nitrogen environment, by (tetrahydro indenyl) (1-normal-butyl indenyl) zirconium dichloride 236mg and methyl Aikyiaiurnirsoxan beta (MAO, Albemarle company, 10% toluene solution) 50ml mixes, and reacts 30 minutes to obtain catalyst solution.To The silicon dioxide of calcining under 220 ° of C of the catalyst solution interpolation 10g of preparation, and implement the ultrasound wave of 1 hour, and lose Abandon supernatant.With the solid particle of hexane (once) wash residual, and it is dried in a vacuum to obtain free flowable solid The supported catalyst of body powder.

C. the copolymerization of ethylene/hexene-1

In addition to using the catalyst of the 61mg prepared in above-mentioned steps, gather according to the polymerization of embodiment 1 Close 3 hours with the polymer obtaining 213g.During 3 hours polyreactions, rate of polymerization is made to keep stable.The catalysis of polymerization is lived Property is 1,170g polymer/g catalyst hour, and the MI (melt index) of the polymer obtained is 0.22g/10min, And the density of the polymer obtained is 0.9305g/cm³。

[embodiment 4]

A. the preparation of (tetrahydro indenyl) (1-ethyl-indenyl) zirconium dichloride

In the 500ml round-bottomed flask of nitrogen environment, double (tetrahydro indenyl) the zirconium dichloride 3.184g (8.0mmol) of interpolation, Zirconium chloride 1.873g (8.4mmol) and toluene 150ml, and react 24 hours under 90 ° of C, stir simultaneously.React it completing After, by filtering product, filtrate is assembled.In 500ml flask, add 1-ethyl-indenyl lithium 2.4g (16mmol), then Add filtrate, and under 90 ° of C, mixture solution is reacted 24 hours, stir simultaneously.Solvent is removed by vacuum draw.This Outward, after the extraction and filtration of 100ml dichloromethane, solvent is again removed.The hexane of 50ml is added with shape to product Become slurry, and filter slurry and wash with 500ml hexane, and be dried in a vacuum to obtain 3.58g's (productivity: 53%) (tetrahydro indenyl) (1-ethyl-indenyl) zirconium dichloride.The 1H NMR of (tetrahydro indenyl) (1-ethyl-indenyl) zirconium dichloride obtained (500MHz,CDCl₃) analysis result be 1.248-1.255 (m, 3, C11H12), 1.466-1.493 (reactant, m), 1.68- 1.72 (reactant, m), 2.325 (m, 1, C9H11), 2.415 (m, 1, C9H11), 2.584 (m, 1, C9H11), 2.703 (m, 1, C9H11),2.97-2.98(m,2,C11H12),4.931(m,2,C9H11),5.50(m,1,C9H11),6.0(m,1, C11H12),6.328(m,1,C11H12),6.592(m,1,C11H12),7.15-7.19(m,2,C11H12),7.53-7.56 (m,2,C11H12)。

B. the preparation of carbon monoxide-olefin polymeric

In the 500ml flask of nitrogen environment, by (tetrahydro indenyl) (1-ethyl-indenyl) zirconium dichloride 130mg and aluminium methyl Oxygen alkane (MAO, Albemarle company, 10% toluene solution) 25ml mixes, and reacts 30 minutes to obtain catalyst solution.To system The silicon dioxide of calcining under 220 ° of C of standby catalyst solution interpolation 5g, and implement the ultrasound wave of 1 hour, and abandon Supernatant.With the solid particle of hexane (once) wash residual, and it is dried in a vacuum to obtain free flowable solid The supported catalyst of powder.

C. the copolymerization of ethylene/hexene-1

In addition to using the catalyst of the 59mg prepared in above-mentioned steps, gather according to the polymerization of embodiment 1 Close 4 hours with the polymer obtaining 190g.During 4 hours polyreactions, rate of polymerization is made somewhat to decay.The catalysis of polymerization is lived Property is 790g polymer/g catalyst hour, and the MI (melt index) of the polymer obtained is 0.18g/10min, and And the density of the polymer obtained is 0.9309g/cm³。

[embodiment 5]

A. the preparation of (tetrahydro indenyl) (2-phenyl indenyl) zirconium dichloride

In the 500ml round-bottomed flask of nitrogen environment, add double (tetrahydro indenyl) zirconium dichloride 1.0g (2.5mmol), chlorine Change zirconium 0.61g (2.75mmol) and toluene 150ml, and react 24 hours under 90 ° of C, stir simultaneously.React it completing After, by filtering product, filtrate is assembled.In 500ml flask, add 2-phenyl indenyl lithium 0.991g (5.0mmol), Then add filtrate, and under 90 ° of C, mixture solution is reacted 24 hours, stir simultaneously.Removed molten by vacuum draw Agent.Additionally, after the extraction and filtration of 100ml dichloromethane, again remove solvent.The hexane of 50ml is added to product To form slurry, and filter slurry and wash with 500ml hexane, and be dried in a vacuum to obtain 0.9g (productivity: 39%) (tetrahydro indenyl) (2-phenyl indenyl) zirconium dichloride.The 1H of (tetrahydro indenyl) (2-phenyl indenyl) zirconium dichloride obtained NMR(500MHz,CDCl₃) analysis result is 1.47-1.49 (m, 2, C9H11), 1.68-1.70 (m, 2, C9H11), 2.41- 2.49(m,2,C9H11),2.68-2.72(m,2,C9H11),5.29-5.31(d,2,C9H11),5.80-5.84(m,1, C9H11),7.20-7.25(m,2,C15H11),7.30-7.33(m,1,C15H11),7.4-7.42(m,2,C15H9),7.58- 7.61(m,2,C15H9),7.67-7.70(m,2,C15H9)。

B. the preparation of carbon monoxide-olefin polymeric

In the 500ml flask of nitrogen environment, by (tetrahydro indenyl) (2-phenyl indenyl) zirconium dichloride 124mg and aluminium methyl Oxygen alkane (MAO, Albemarle company, 10% toluene solution) 25ml mixes, and reacts 30 minutes to obtain catalyst solution.To system The silicon dioxide of calcining under 220 ° of C of standby catalyst solution interpolation 5g, and implement the ultrasound wave of 1 hour, and abandon Supernatant.With the solid particle of hexane (once) wash residual, and it is dried in a vacuum to obtain free flowable solid The supported catalyst of powder.

C. the copolymerization of ethylene/hexene-1

In addition to using the catalyst of the 60mg prepared in above-mentioned steps, gather according to the polymerization of embodiment 1 Close 3 hours with the polymer obtaining 70g.During 3 hours polyreactions, rate of polymerization is made to keep stable.The catalysis of polymerization is lived Property is 400g polymer/g catalyst hour, and the MI (melt index) of the polymer obtained is 0.11g/10min, and And the density of the polymer obtained is 0.9257g/cm³。

[comparative example]

A. the preparation of carbon monoxide-olefin polymeric

In the 500ml flask of nitrogen environment, will double (tetrahydro indenyl) zirconium chloride 84mg and MAO (MAO, Albemarle company, 10% toluene solution) 20ml mixing, and stir 30 minutes to obtain catalyst solution.Catalysis to preparation The silicon dioxide of calcining under 220 ° of C of agent solution interpolation 4g, and implement the ultrasound wave of 1 hour, and abandon supernatant.With The solid particle of hexane (once) wash residual, and be dried in a vacuum to obtain the negative of free flowable pressed powder Carried catalyst.

B. the copolymerization of ethylene/hexene-1

In addition to using the catalyst of the 105mg prepared in above-mentioned steps, gather according to the polymerization of embodiment 1 Close 1 hour with the polymer obtaining 123g.During the polymerization of 1 hour, rate of polymerization promptly decays, although initial catalyst is lived Property high.The catalysis activity of polymerization is 1,170g polymer/g catalyst hour, and MI (the melted finger of the polymer obtained Number) it is 0.11g/10min, and the density of the polymer obtained is 0.9226g/cm³。

Claims

1. olefine polymerizing process, it is included in selected from (tetrahydro indenyl) (indenyl) zirconium dichloride and (tetrahydro indenyl) (2-methyl indenes Base) zirconium dichloride metallocene compound in the presence of be polymerized the step of at least one alkene.

2. olefine polymerizing process as claimed in claim 1, wherein said alkene is the aliphatic alpha-alkene of 2 to 12 carbon atoms Hydrocarbon.

3. olefine polymerizing process as claimed in claim 1, wherein said polyreaction is solution phase, slurry phase, body phase or gas Phase polymerization reaction.

4. olefine polymerizing process as claimed in claim 1, the density of wherein said alkene is 0.91g/cm³To 0.94g/cm³。