Nano-Linked Metallocene Catalyst Compositions and Their Polymer Products

Abstract

The present invention provides polymerization catalyst compositions employing novel dinuclear metallocene compounds. Methods for making these new dinuclear metallocene compounds and for using such compounds in catalyst compositions for the polymerization and copolymerization of olefins are also provided.

1 - 29 . (canceled) 
     
     
         30 . A compound having the formula: 
       
         
           
           
               
               
           
         
       
       wherein:
 X 1  and X 2  independently are a halide or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof; 
 X 3  is a substituted fluorenyl group, any substituents on X 3  other than a bridging group independently are a hydrogen atom or a substituted or unsubstituted alkyl or alkenyl group; 
 X 4  is a substituted cyclopentadienyl group, any substituents on X 4  other than the bridging group and an alkenyl linking group independently are a hydrogen atom or a substituted or unsubstituted alkyl or alkenyl group; 
 A 1  is a carbon bridging atom with two phenyl substituents; 
 M is Zr, Hf, or Ti; 
 E is carbon; 
 R X , R Y , and R Z  are hydrogen atoms; and 
 n is 1, 2, 3, 4, or 5. 
 
     
     
         31 . The compound of  claim 30 , wherein X 1  and X 2  independently are a methyl group, a phenyl group, or a halide. 
     
     
         32 . The compound of  claim 30 , wherein X 1  and X 2  are chlorine atoms. 
     
     
         33 . The compound of  claim 30 , wherein each substituent on X 3  other than the bridging group, and on X 4  other than the bridging group and the alkenyl linking group, independently is a hydrogen atom, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, or a hexyl group. 
     
     
         34 . The compound of  claim 30 , wherein a substituent on X 3  is a t-butyl group. 
     
     
         35 . The compound of  claim 30 , wherein M is Zr. 
     
     
         36 . The compound of  claim 30 , wherein M is Hf. 
     
     
         37 . The compound of  claim 30 , wherein M is Ti. 
     
     
         38 . A compound having the formula: 
       
         
           
           
               
               
           
         
       
       wherein:
 X 1  and X 2  independently are a halide or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof; 
 X 3  is a substituted indenyl or fluorenyl group, any substituents on X 3  other than a bridging group independently are a hydrogen atom or a substituted or unsubstituted alkyl or alkenyl group; 
 X 4  is a substituted cyclopentadienyl, indenyl, or fluorenyl group, any substituents on X 4  other than the bridging group and an alkenyl linking group independently are a hydrogen atom or a substituted or unsubstituted alkyl or alkenyl group; 
 A 1  is a substituted or unsubstituted bridging group comprising either a cyclic group of 5 to 8 carbon atoms, a bridging chain of 2 to 5 carbon atoms, or a carbon, silicon, germanium, tin, boron, nitrogen, or phosphorus bridging atom, any substituents on A 1  independently are a hydrogen atom, or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof; 
 M is Zr, Hf, or Ti; 
 E is carbon or silicon; 
 R X , R Y , and R Z  independently are a hydrogen atom, or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof; and 
 n is an integer in a range from 0 to 12, inclusive. 
 
     
     
         39 . The compound of  claim 38 , wherein:
 E is carbon; and   R X , R Y , and R Z  independently are a hydrogen atom or a methyl group.   
     
     
         40 . The compound of  claim 39 , wherein:
 X 1  and X 2  independently are a methyl group, a phenyl group, a benzyl group, or a halide;   X 3  is a substituted indenyl or fluorenyl group, any substituents on X 3  other than the bridging group independently are a hydrogen atom, a methyl group, an ethyl group, a propyl group, a n-butyl group, a t-butyl group, or a hexyl group;   X 4  is a substituted cyclopentadienyl, indenyl, or fluorenyl group, any substituents on X 4  other than the bridging group and the alkenyl linking group independently are a hydrogen atom, a methyl group, an ethyl group, a propyl group, a n-butyl group, a t-butyl group, or a hexyl group;   A 1  comprises either a bridging chain of 2 to 5 carbon atoms or a carbon bridging atom, any substituents on A 1  independently are a hydrogen atom, a methyl group, a phenyl group, or a benzyl group;   R X , R Y , and R Z  are hydrogen atoms; and   n is 1, 2, 3, 4, or 5.   
     
     
         41 . The compound of  claim 40 , wherein A 1  is a carbon bridging atom with two methyl, phenyl, or benzyl substituents. 
     
     
         42 . A compound having the formula: 
       
         
           
           
               
               
           
         
       
       wherein:
 X 1  and X 2  independently are a halide or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof; 
 X 3  is a substituted cyclopentadienyl, indenyl, or fluorenyl group, at least one substituent on X 3  other than a bridging group is a substituted or unsubstituted alkyl or alkenyl group; 
 X 4  is a substituted cyclopentadienyl, indenyl, or fluorenyl group, any substituents on X 4  other than the bridging group and an alkenyl linking group independently are a hydrogen atom or a substituted or unsubstituted alkyl or alkenyl group; 
 A 1  is a substituted or unsubstituted bridging group comprising either a cyclic group of 5 to 8 carbon atoms, a bridging chain of 2 to 5 carbon atoms, or a carbon, silicon, germanium, tin, boron, nitrogen, or phosphorus bridging atom, any substituents on A 1  independently are a hydrogen atom, or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof; 
 M is Zr, Hf, or Ti; 
 E is carbon or silicon; 
 R X , R Y , and R Z  independently are a hydrogen atom, or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof; and 
 n is an integer in a range from 0 to 12, inclusive. 
 
     
     
         43 . The compound of  claim 42 , wherein:
 E is carbon; and   R X , R Y , and R Z  independently are a hydrogen atom or a methyl group.   
     
     
         44 . The compound of  claim 43 , wherein:
 X 1  and X 2  independently are a methyl group, a phenyl group, a benzyl group, or a halide;   at least one substituent on X 3  is a methyl group, an ethyl group, a propyl group, a n-butyl group, a t-butyl group, or a hexyl group;   A 1  comprises either a bridging chain of 2 to 5 carbon atoms or a carbon bridging atom, any substituents on A 1  independently are a hydrogen atom, a methyl group, a phenyl group, or a benzyl group;   R X , R Y , and R Z  are hydrogen atoms; and   n is 1, 2, 3, 4, or 5.   
     
     
         45 . The compound of  claim 44 , wherein A 1  is a carbon bridging atom with two methyl, phenyl, or benzyl substituents. 
     
     
         46 . The compound of  claim 42 , wherein:
 E is carbon;   X 1  and X 2  are methyl groups, phenyl groups, or chlorine atoms;   X 3  and X 4  independently are a substituted cyclopentadienyl group or a substituted fluorenyl group;   A 1  comprises a carbon bridging atom;   R X , R Y , and R Z  are hydrogen atoms; and   n is 1, 2, 3, 4, or 5.