Metallocenes containing ligands of 2-substituted indenyl derivatives, process for their preparation, and their use as catalysts

Abstract

The novel metallocenes of the formula I in which, preferably, M 1 is Zr or Hf, R 1 and R 2 are alkyl or halogen, R 3 and R 4 are hydrogen, R 5 and R 6 are alkyl or haloalkyl, —(CR 8 R 9 ) m —R 7 —(CR 8 R 9 ) n — is a single- or multi-membered chain in which R 7 may also be a (substituted) hetero atom, m+n is zero or 1, and R 10 is hydrogen, form, together with aluminoxanes as cocatalysts, a very effective catalyst system for the preparation of polyolefins of high stereospecificity and high melting point.

1. A compound of the formula I for preparing essentially isotactic olefin polymers 
                 
 
       in which
 M 1  is a metal from group IVb, Vb or VIb of the Periodic Table  
 R 1  and R 2  are identical or different and are a hydrogen atom, a C 1 -C 10 -alkyl group, a C 1 -C 10 -alkoxy group, a C 6 -C 10 -aryl group, a C 6 -C 10 -aryloxy group, a C 2 -C 10 -alkenyl group, a C 7 -C 40 -arylalkyl group, a C 7 -C 40 -alkylaryl group, a C 8 -C 40 -arylalkenyl group or a halogen atom,  
 R 3    is a hydrogen atom, a halogen atom, a C   2   -C   10 - alkyl group, a C   1   -C   10 - alkyl group which is halogenated, a C   6   -C   10 - aryl group, an —NR   2   15   , —SR   15   , —OSiR   3   15   , —SiR   3   15    or —PR   2   15    radical in which R   15    is a halogen atom, a C   1   -C   10 - alkyl group or a C   6   -C   10 - aryl group,   
 R 3  and  R 4  are identical or different and areis a hydrogen atom, a halogen atom, a C 1 -C 10 -alkyl group, which is optionally halogenated, a C 6 -C 10 -aryl group, an —NR 2   15 , —SR 15 , —OSiR 3   15 , —SiR 3   15  or —PR 2   15  radical in which R 15  is a halogen atom, a C 1 -C 10 -alkyl group or a C 6 -C 10 -aryl group,  
 R 5  and R 6  are identical or different and are as defined for R 3  and  R 4 , with the proviso that R 5  and R 6  are not hydrogen,  
 R 7  is 
                 
 
 
       ═BR 11 , ═AlR 11 , —Ge—, —Sn—, —O—, —S—, ═SO, ═SO 2 , ═NR 11 , ═CO, ═PR 11  or ═P(O)R 11 ,
 where  
 R 11 , R 12  and R 13  are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 10 -alkyl group, a C 1 -C 10 -fluoroalkyl group, a C 6 -C 10 -aryl group, a C 6 -C 10 -fluoroaryl group, a C 1 -C 10 -alkoxy group, a C 2 -C 10 -alkenyl group, a C 7 -C 40 -arylalkyl group, a C 8 -C 40 -arylalkenyl group or a C 7 -C 40 -alkylaryl group, or a pair of substituents R 11  and R 12  or R 11  and R 13  in each case with the atoms connecting them, form a ring,  
 M 2  is silicon, germanium or tin,  
 R 8  and R 9  are identical or different and are as defined for R 11    
 m and n are identical or different and are zero, 1 or 2, m plus n being zero, 1 or 2,  
 the radicals R 10  are identical or different and are as defined for R 11 , R 12  and R 13 ,  
   rings A are saturated or aromatic,    
   p is  8 , when rings A are saturated, and    
   p is  4 , when rings A are aromatic.   
 
     
     
       2. A compound of the formula I as claimed in  claim 1 , wherein, in the formula I, M 1  is Zr or Hf, R 1  and R 2  are identical or different and are methyl or chlorine, R 3  or R 4  are hydrogen, R 5  and R 6  are identical or different and are methyl, ethyl or trifluoromethyl, R 7  is a 
                 
 
       n plus m is zero or 1, and R 10  is hydrogen. 
     
     
       3. A compound of the formula I as claimed in  claim 1  wherein the compound is rac-dimethylsilyl(2-methyl-4,5,6,7-tetrahydro-1-indenyl) 2 zirconium dichloride, racethylene(2-methyl-4,5,6,7-tetrahydro-1-indenyl) 2 zirconium dichloride, rac-dimethylsilyl (2-methly-4,5,6,7-tetrahydro-1-indenyl) 2 dimethylzirconium or racethylene(2-methyl-4,5,6,7-tetrahydro-1-indenyl) 2 dimethylzirconium. 
     
     
       4. A compound as claimed in  claim 1 , wherein M 1  is zirconium, hafnium or titanium. 
     
     
       5. A compound as claimed in  claim 1 , wherein R 1  and R 2  are identical or different and are a hydrogen atom, a C 1 -C 3 -alkyl group, a C 1 -C 3 -alkoxy group, a C 6 -C 8 -aryl group, a C 6 -C 6 -arloxy group, a C 2 -C 4 -alkenyl group, a C 7 -C 10 -arylalkyl group, a C 7 -C 12 -alkylaryl group, a C 8 -C 12 -arylalkenyl group or chlorine. 
     
     
       6. A compound as claimed in  claim 1 , wherein R 3  is a C 4 - alkyl group, C   1   -C   4 - alkyl group which is halogenated, a C   6   -C   8 - aryl group, an —NR   2   15   , —SR   15   , —OSiR   3   15   , —SiR   3   15    or —PR   2   15    radical and R   4  are identical and different and are  is a hydrogen atom, a fluorine, chlorine or bromine atom, a C 1 -C 4 -alkyl group, which may be halogenated, a C 6 -C 8 -aryl group, an —NR 2   15 , —SR 15 , —OSiR 3   15 , —SiR 3   15  or —PR 2   15  radical in which R 15  is a chlorine atom, or a C 1 -C 3 -alkyl group or a C 6 -C 8 -aryl group. 
     
     
       7. A compound as claimed in  claim 1 ,  of the formula ( I ) for preparing essentially isotactic olefin polymers 
                 
 
       
         in which  
         
           M 
           1  
           is a metal from group IVb, Vb or VIb of the Periodic Table 
         
           R   1    and R   2    are identical or different and are a hydrogen atom, a C   1   -C   10 - alkyl group, a C   1   -C   10 - alkoxy group, a C   6   -C   10 - aryl group, a C   6   -C   10 - aryloxy group, a C   2   -C   10 - alkenyl group, a C   7   -C   40 - arylalkyl group, a C   7   -C   40 - alkylaryl group, a C   8   -C   40 - arylalkenyl group or a halogen atom,   
         R 3  and R 4  are hydrogen,  
           R   5    and R   6    are identical or different and are a halogen atom, a C   1   -C   10 - alkyl group, which is optionally halogenated, a C   6   -C   10 - aryl group, an —NR   2   15   , —SR   15   , —OSiR   3   15   , —SiR   3   15    or —PR   2   15    radical in which R   15    is a halogen atom, a C   1   -C   10 - alkyl group or a C   6   -C   10 - aryl group                     
       
         ═BR   11   , ═AlR   11   , —Ge—, —Sn—, —O—, —S—, ═SO, ═SO   2   , ═NR   11   , ═CO, ═PR   11    or ═P ( O ) R   11   , where      R   11   , R   12    and R   13    are identical or different and are a hydrogen atom, a halogen atom, a C   1   -C   10 - alkyl group, a C   1   -C   10 - fluoroalkyl group, a C   6   -C   10 - aryl group, a C   6   -C   10 - fluoroaryl group, a C   1   -C   10 - alkoxy group, a C   2   -C   10 - alkenyl group, a C   7   -C   40 - arylalkyl group, a C   8   -C   40 - arylalkenyl group or a C   7   -C   40 - alkylaryl group, or a pair of substituents R   11    and R   12  --  or R   11    and R   13    in each case with the atoms connecting them, form a ring,        M   2    is silicon, germanium or tin,        R   8    and R   9    are identical or different and are as defined for R   11       m and n are identical or different and are zero,  1  or  2 , m plus n being zero,  1  or  2 ,        the radicals R   10    are identical or different and are as defined for R   11   , R   12    and R   13   ,        rings A are saturated or aromatic,        p is  8 , when rings A are saturated, and        p is  4 , when rings A are aromatic.     
     
     
       8. A compound as claimed in  claim 1 , wherein R 5  and R 6  are identical. 
     
     
       9. A compound as claimed in  claim 1 , wherein R 5  and R 6  are (C 1 -C 4 )-alkyl, which may be halogenated with methyl. 
     
     
       10. A compound as claimed in  claim 1 , wherein R 11 , R 12  and R 13  are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 4 -alkyl group, a CF 3  group, a C 6 -C 8 -aryl group, a pentafluorophenyl group, a C 1 -C 4 -alkoxy group, a C 2 -C 4 -alkenyl group, a C 7 -C 10 -arylalkyl group, a C 8 -C 12 -arylalkenyl group of a C 7 -C 12 -alkylaryl group, or R 11  and R 12  or R 11  and R 13 , in each case together with the atoms connecting them, form a ring. 
     
     
       11. A compound as claimed in  claim 1 , wherein M 2  is silicon or germanium. 
     
     
       12. A compound as claimed in  claim 1 , wherein R 7  is ═CR 11 R 12 , ═SiR 11 R 12 , ═GeR 11 R 12 , —O—, —S—, ═SO, —PR 11  or ═P(O)R 11 . 
     
     
       13. A compound as claimed in  claim 1 , wherein m and n are identical or different and are zero or 1. 
     
     
       14. A compound as claimed in  claim 1 , wherein m plus n is zero or 1. 
     
     
       15. A compound as claimed in  claim 1 , wherein R 10  is hydrogen or C 1 -C 4 -alkyl groups. 
     
     
       16. A compound of the formula ( I )′
                   
       
         in which  
         
           M 
           1  
           is a metal from group IVb, Vb or VIb of the Periodic Table,  
         
           R   1    and R   2    are identical or different and are a hydrogen atom, a C   1   -C   10 - alkyl group, a C   1   -C   10 - alkoxy group, a C   6   -C   10 - aryl group, a C   6   -C   10 - aryloxy group, a C   2   -C   10 - alkenyl group, a C   7   -C   40 - arylalkyl group, a C   7   -C   40 - alkylaryl group, a C   8   -C   40 - arylalkenyl group or a halogen atom,    
           R   3    is a hydrogen atom, a halogen atom, a C   2   -C   10 - alkyl group, a C   1   -C   10 - alkyl group which is halogenated, a C   6   -C   10 - aryl group, an —NR   2   15   , —SR   15   , —OSiR   3   15   , —SiR   3   15    or —PR   2   15    radical in which R   15    is a halogen atom, a C   1   -C   10 - alkyl group or a C   6   -C   10 - aryl group,    
           R   4    is a hydrogen atom, a halogen atom, a C   1   -C   10 - alkyl group, which is optionally halogenated, a C   6   -C   10 - aryl group, an —NR   2   15   , —SR   15   , —OSiR   3   15   , —SiR   3   15    or —PR   2   15    radical in which R   15    is a halogen atom, a C   1   -C   10 - alkyl group or a C   6   -C   10 - aryl group,    
         
           R 
           5  
           and R 
           6  
           are identical or different and are as defined for R 
           3  
           and R 
           4 
           , with the proviso that R 
           5  
           and R 
           6  
           are not hydrogen, 
         
         
           R 
           7  
           is  
           
             
             
                 
                 
             
           
         
       
         ═BR   11   , ═AlR   11   , —Ge—, —Sn—, —O—, —S—, ═SO, ═SO   2   , ═NR   11   , ═CO, ═PR   11    or ═P ( O ) R   11   ,      where        R   11   , R   12    and R   13    are identical or different and are a hydrogen atom, a halogen atom, a C   1   -C   10 - alkyl group, a C   1   -C   10 - fluoroalkyl group, a C   6   -C   10 - aryl group, a C   2   -C   10 - alkenyl group, a C   7   -C   40 - arylalkyl group, a C   8   -C   40 - arylalkenyl group or a C   7   -C   40 - alkylaryl group, or a pair of substituents R   11    and R   12    or R   11    and R   13   , in each case with the atoms connecting them, form a ring,        M   2    is silicon, germanium or tin,        R   8    and R   9    are identical or different and are as defined for R   11        m and n are identical or different and are zero,  1  or  2 , m plus n being zero,  1  or  2 , the radicals R   10    are the same or different and are as defined for R   11   , R   12    and R   13 .   
     
     
       17. A compound as claimed in  claim 16 , wherein:
   M   1    is titanium, zirconium, hafnium, vanadium, niobium, or tantalum,        R   1    and R   2    are identical or different and are methyl or halogen,        R   3    and R   4    are hydrogen,        R   5    and R   6    are identical or different and are methyl, ethyl, or trifluoromethyl,        R   7    is a radical of the formula                         where M   11    is silicon or germanium, and        R   8    and R   9    are identical or different and are hydrogen or C   1   -C   10 - alkyl.     
     
     
       18. A catalyst composition comprising the combination comprising a compound of  claim 16  and a cocatalyst. 
     
     
       19. A catalyst composition comprising the combination comprising a compound of  claim 16  and an aluminoxane. 
     
     
       20. A process for polymerizing an olefin monomer, comprising the step of carrying out the polymerization in the presence of a catalyst composition of  claim 19 . 
     
     
       21. A process for polymerizing an olefin monomer, comprising the step of carrying out the polymerization in the presence of a catalyst composition of  claim 20 . 
     
     
       22. The compound as claimed in  claim 1 , wherein R 3    is a hydrogen atom, a halogen atom, a C   1   -C   10 - alkyl group which is halogenated, a C   6   -C   10 - aryl group, an —NR   2   15   , —SR   15   , —OSiR   3   15   , —SiR   3   15    or —PR   2   15    radical in which R   15    is a halogen atom, a C   1   -C   10 - alkyl group or a C   6   -C   10 - aryl group.   
     
     
       23. The compound as claimed in  claim 1 , wherein R 3    is a hydrogen atom, a halogen atom, a C   6   -C   10 - aryl group, an —NR   2   15   , —SR   15   , —OSiR   3   15   , —SiR   3   15    or —PR   2   15    radical in which R   15    is a halogen atom, a C   1   -C   10 - alkyl group or a C   6   -C   10 - aryl group.