Multicyclic metallocycle metallocenes and their use

Abstract

A process for producing a new metallocene comprising reacting a first metallocene which has a cyclodiene group having an olefinically unsaturated substituent with about two molar equivalents of an alkali metal alkyl, catalyst systems resulting from the combination of the resulting metallocene and an organoaluminum cocatalysts, and polymerization processes using such catalyst systems are disclosed.

That which is claimed is:  
     
         1 . A process for producing a metallocene comprising reacting a first metallocene having an alkenyl group attached to a cyclodienyl group of the metallocene with about two molar equivalents of an alkali metal alkyl having at least 4 carbon atoms.  
     
     
         2 . A process according to  claim 1  wherein the alkali metal alkyl is n-butyl lithium.  
     
     
         3 . A process according to  claim 2  wherein the alkenyl group is a straight chain alkenyl having 3 to 5 carbon atoms and terminal olefinic unsaturation.  
     
     
         4 . A process according to  claim 3  wherein the alkenyl group is 3-butenyl.  
     
     
         5 . A process according to  claim 4  wherein the metal of the first metallocene is zirconium.  
     
     
         6 . A process according to  claim 5  wherein the first metallocene used is 1-(9-fluorenyl)-1-(3-butenylcyclopentadienyl)-1,1-dimethyl methane zirconium dichloride.  
     
     
         7 . A process according to  claim 5  wherein the first metallocene used is (3-butenylcyclopentadienyl)(t-butyl amido)dimethyl silane titanium dichloride.  
     
     
         8 . A metallocene produced by the process of  claim 1 .  
     
     
         9 . A metallocene produced by the process of  claim 5 .  
     
     
         10 . A muticyclic metallocycle metallocene having the formula  
       
         
           
           
               
               
           
         
       
       wherein L is a group having a cyclodienyl skeleton, x is 0 or 1, n is 1 to 3, m is 1 to 4, Y is a structural unit connecting L to L′, if x is 1 then L′ is selected from group consisting of monovalent radicals having a cyclodienyl skeleton and divalent radicals selected from those having the formula —NR—,—PR—, —O—, and —S—, and if x is 0 then L′ is selected from cyclodienyl compounds pi bonded to M, and M is a transition metal.  
     
     
         11 . A metallocene according to  claim 11  wherein L and L′ are the same or different and are selected from the group consisting of cyclopentadienyl, indenyl, and fluorenyl either unsubstituted or substituted with one or more hydrocarbyl substitutents, M is selected from Zr, Hf, and Ti.  
     
     
         12 . A metallocene according to  claim 11  wherein M is Zr.  
     
     
         13 . A metallocene according to  claim 12  wherein x is 1 and Y is selected from the divalent radicals selected from the group consisting of —CH 2 —, —CR 2 —, and —SiR 2 —.  
     
     
         14 . A metallocene according to  claim 13  wherein n is 2, L is cyclopentadienyl, L′ is fluorenyl, and Y is dimethylmethylene.  
     
     
         15 . A catalyst system useful for the polymerization of olefins comprising the product resulting from the combination of the metallocene produced by the process of  claim 14  and an organometallic cocatalyst.  
     
     
         16 . A catalyst system of useful for the polymerization of olefins comprising the product prepared by combining the metallocene produced by the process of  claim 14  and the organometallic cocatalyst and conducting a prepolymerization in the presence of an olefin to produce a particulate prepolymerized solid catalyst system.  
     
     
         17 . A catalyst system of  claim 16  wherein the cocatalyst comprises a pentafluorophenyl borate.  
     
     
         18 . A catalyst system of  claim 16  wherein the cocatalyst comprises an alkylaluminoxane.  
     
     
         19 . A process for producing a polymer comprising contacting an olefin with the catalyst system of  claim 18  under polymerization conditions.  
     
     
         20 . A process for producing a polymer comprising contacting an olefin with the catalyst system of  claim 15  under polymerization conditions.  
     
     
         21 . A catalyst system useful for the polymerization of olefins comprising the product resulting from the combination of the metallocene produced by the process of  claim 1  and an organometallic cocatalyst.  
     
     
         22 . A catalyst system according to  claim 21  wherein the alkenyl group of the first metallocene is 3-butenyl.  
     
     
         23 . A catalyst system according to  claim 22  wherein the metal of the first metallocene is zirconium.  
     
     
         24 . A catalyst system according to  claim 23  wherein the first metallocene is 1-(9-fluorenyl)-1-(3-butenylcyclopentadienyl)-1,1-dimethyl methane zirconium dichloride  
     
     
         25 . A process for producing a polymer comprising contacting an olefin with the catalyst system of claim  25 .