Preparation and Use of Tetrasubstituted Fluorenyl Catalysts for Polymerization of Olefins

Abstract

Catalyst compositions and processes for the polymerization of ethylenically unsaturated monomers to produce polymers, including copolymers or homopolymers. Such monomers include ethylene, C 3+ alpha olefins and substituted vinyl compounds, such as styrene and vinyl chloride. The polymerization catalyst characterized by the formula B(FluL)MQ n in which Flu is a fluorenyl group substituted at at least the 2,7- and 3,6-positions by hydrocarbyl groups, preferably relatively bulky hydrocarbyl groups. L is a substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl group or a heteroorgano group, XR, in which X is a heteroatom from Group 15 or 16 of the Periodic Table of Elements, such as nitrogen, R is an alkyl group, a cycloalkyl group or an aryl group and B is a structural bridge extending between the groups L and Flu, which imparts stereorigidity to the ligand structure, M is a Group 4 or Group 5 transition metal, such as titanium, zirconium or hafnium and Q is selected from the group consisting of chlorine, bromine, iodine, an alkyl group, an amino group, an aromatic group and mixtures thereof, with n being 1 or 2.

1 - 5 . (canceled) 
     
     
         6 . A metallocene component for an olefin polymerization catalyst characterized by the formula:
   B(FluL)MQ n   (3)
   
       wherein:
 (a) Flu is a fluorenyl group substituted at least the 2,7 position and the 3,6 position, wherein said fluorenyl group Flu is substituted at each of the 2 and 7 positions with a C1-C3 alkyl group and at each of the 3 and 6 positions with a bulky hydrocarbon group containing at least 4 carbon atoms; 
 (b) L is a substituted or an unsubstituted cyclopentadienyl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted fluorenyl group, or a heteroorgano group XR2 in which X is a heteroatom from Group 15 or 16 of the Periodic Table, and R is an alkyl group, a cycloalkyl group or an aryl group containing from 1 to 20 carbon atoms; 
 (c) B is a structural bridge between L and Flu imparting stereorigidity to the ligand structure (FluL); 
 (d) M is a Group 4 or Group 5 transition metal; 
 (e) Q is selected from the group consisting of Cl, Br, I, an alkyl group, an amino group, an aromatic group and mixtures thereof; and 
 (f) n is 1 or 2. 
 
     
     
         7 . A metallocene component for an olefin polymerization catalyst characterized by the formula:
   B(FluL)MQ n   (3)
   
       wherein:
 (g) Flu is a fluorenyl group substituted at least the 2,7 position and the 3,6 position, wherein the substitution at each of the 3 and 6 positions is a tertiary butyl group, 
 (h) L is a heteroorgano group XR2 and wherein X is N, P, O or S, and R is an alkyl, cycloalkyl or aryl group; 
 (i) B is a structural bridge between L and Flu imparting stereorigidity to the ligand structure (FluL); 
 (j) M is a Group 4 or Group 5 transition metal; 
 (k) Q is selected from the group consisting of Cl, Br, I, an alkyl group, an amino group, an aromatic group and mixtures thereof; and 
 (l) n is 1 or 2. 
 
     
     
         8 . The component of  claim 7  wherein X is N and R is a mononuclear aromatic group, or an alkyl or cycloalkyl group containing from 1 to 20 carbon atoms. 
     
     
         9 . (canceled) 
     
     
         10 . (canceled) 
     
     
         11 . A metallocene component for an olefin polymerization catalyst characterized by the formula: 
       
         
           
           
               
               
           
         
       
       wherein:
 Ar is a phenyl group or substituted phenyl group; 
 R′ is a C1-C4 alkyl group or an aryl group; 
 n is the number of substituents, from 0 to 4; 
 E is a —C— group or an —Si— group; 
 R1 and R2 are each independently a hydrogen, a C1-C10 alkyl group, or a cycloalkyl group, or an aryl group; 
 M is titanium, zirconium or hafnium; and 
 Q is chlorine, a methyl group or a phenyl group; and 
 wherein the cyclopentadienyl group is unsubstituted (n=0), a disubstituted cyclopentadienyl group (n=2) or a tetrasubstituted cyclopentadienyl group (n=4) wherein said metallocene component exhibits bilateral symmetry, or 
 wherein said cyclopentadienyl group is monosubstituted (n=1) or trisubstituted (n=3) wherein said metallocene component exhibits a non-bilateral symmetry. 
 
     
     
         12 - 35 . (canceled)