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. The polymerization catalyst characterized by the formula B(FluL)MQ n in which Flu is a fluorenyl group substituted at least the 2,7- and 3,6-positions by 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, 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, 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 . 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; 
 (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. 
 
     
     
         2 . The metallocene component of  claim 1  wherein the fluorenyl group Flu is substituted with substituents at the 2,7 positions which are bulkier than the substituents at the 3,6 positions. 
     
     
         3 . The metallocene component of  claim 1  wherein the fluorenyl group Flu is substituted with an aryl group at each of the 2 and 7 positions and with a lower molecular weight substituent at each of the 3 and 6 positions. 
     
     
         4 . The metallocene component of  claim 3  wherein said fluorenyl group Flu is substituted at each of the 2 and 7 positions with a phenyl or a substituted phenyl group and at each of the 3 and 6 positions with a bulky hydrocarbon group containing at least four carbon atoms. 
     
     
         5 . The component of  claim 4  wherein said fluorenyl group Flu is substituted at each of the 3 and 6 positions with a tertiary butyl group. 
     
     
         6 . The metallocene component of  claim 1  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. 
     
     
         7 . The component of  claim 5  wherein L is a heteroorgano group, XR2 and wherein X is N, P, O or S, and R is an alkyl, cycloalkyl or aryl group. 
     
     
         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 . The metallocene component of  claim 1  wherein B(FluL)MQn is characterized by the formula: 
       
         
           
           
               
               
           
         
       
       wherein Ar is a phenyl group or substituted phenyl group. 
     
     
         10 . The metallocene component of  claim 1  wherein B(FluL)MQn is characterized by the formula: 
       
         
           
           
               
               
           
         
       
       wherein:
 Ar is a phenyl group or a substituted phenyl group; and 
 R is an alkyl group having from 1 to 20 carbon atoms or an aryl group having from 6 to 20 carbon atoms. 
 
     
     
         11 . The metallocene component of  claim 1  wherein B(FluL)MQn incorporates a cyclopentadienyl group and is 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. 
 
     
     
         12 . The metallocene component of  claim 11  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. 
     
     
         13 . The metallocene component of  claim 11  wherein said cyclopentadienyl group is monosubstituted (n=1) or trisubstituted (n=3) wherein said metallocene component exhibits a non-bilateral symmetry. 
     
     
         14 . The metallocene component of  claim 1  wherein B(FluL)MQn incorporates a cyclopentadienyl group and is characterized by the formula: 
       
         
           
           
               
               
           
         
       
       wherein:
 Ar is a phenyl group or substituted phenyl group; 
 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. 
 
     
     
         15 . The metallocene component of  claim 1  wherein B(FluL)MQn incorporates a cyclopentadienyl group and is characterized by the formula: 
       
         
           
           
               
               
           
         
       
       wherein:
 Ar is a phenyl group or substituted phenyl group; 
 R1 and R2 are each independently a hydrogen, a C1-C10 alkyl group, or a cycloalkyl group, or an aryl group; 
 E is a —C— group or an —Si— group; 
 M is titanium, zirconium or hafnium; and 
 Q is chlorine, a methyl group or a phenyl group. 
 
     
     
         16 . The metallocene catalyst component of  claim 1  wherein B(FluL)MQn incorporates an indenyl group and is further characterized by the formula: 
       
         
           
           
               
               
           
         
       
       wherein:
 Ar is a phenyl group or substituted phenyl group; 
 Ind is an indenyl or substituted indenyl group; 
 E is a —C— group or an —Si— group; 
 each of R1 and R2 is a C1-C4 alkyl group; 
 M is titanium, zirconium or hafnium; and 
 Q is chlorine, a methyl group or a phenyl group. 
 
     
     
         17 . The metallocene component of  claim 16  wherein said indenyl group is a tetrahydroindenyl group which is substituted or unsubstituted. 
     
     
         18 . The metallocene component of  claim 17  wherein said indenyl group is an unsubstituted indenyl group or an unsubstituted tetrahydroindenyl group. 
     
     
         19 . The metallocene component of  claim 1  wherein B(FluL)MQn is further characterized by the formula: 
       
         
           
           
               
               
           
         
       
       wherein:
 Flu is a fluorenyl or a substituted fluorenyl group; 
 E is a —C— group or an —Si— group; 
 each of R1 and R2 is a C1-C4 alkyl group; 
 M is titanium, zirconium or hafnium; and 
 Q is chlorine, a methyl group or a phenyl group. 
 
     
     
         20 . The metallocene component of  claim 19  wherein Flu is an unsubstituted fluorenyl group or a substituted fluorenyl group wherein the metallocene component exhibits bilateral symmetry. 
     
     
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