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  and R 4  are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 10 -alkyl group, which is optionally halogenated, 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  radicals 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 
                 
 
 
       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 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, and  
 the radicals R 10  are identical or different and are as defined for R 11 , R 12  and R 13 .  
 
     
     
       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, rac-ethylene(2-methyl-4,5,6,7-tetrahydro-1-indenyl) 2 -zirconium dichloride, rac-dimethylsilyl (2-methyl-4,5,6,7-tetrahydro-1-indenyl) 2 dimethylzirconium or rac-ethylene(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 8 -aryloxy 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  and R 4  are identical or different and are 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, a —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 , wherein R 3  and R 4  are hydrogen. 
     
     
       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. 
     
     
       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 or 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 II
                   
       
         wherein:  
         
           M 
           3  
           is an alkali metal;  
         
           R   3    and R   4    are identical or different and are 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    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 , and  
         
           the radicals R   10    are identical or different and are as defined for R   11   , R   12    and R   13 . 
       
     
     
       17. A compound of formula II as claimed in  claim 16 , said compound having the formula:
   {(   2   - Me - Ind ) 2   CH   2   CH   2   }M   2   3 ,    
       
         in which Me is methyl, and Ind is the indenyl group of said formula II. 
       
     
     
       18. A compound of the formula
                   
       
         wherein  
           R   3    represent hydrogen; halogen, C   1   -C   10 - alkyl, which is optionally halogenated; C   6   -C   10 - aryl, an —NR   2   15   , —SR   15   , —OSiR   3   15   , —SiR   3   15    or PR   2   15    radical in which R   15    represents halogen, C   1   -C   10 - alkyl or C   6   -C   10 - aryl;    
           R   5    is a halogen atom, a C   2   -C   10 - alkyl group, a C   1   -C   10 - alkyl group which is halogenated, a 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, and    
           R   10    are identical or different and are hydrogen, halogen, C   1   -C   10 - alkyl, C   1   -C   10 - fluoroalkyl, C   6   -C   10 - aryl, C   6   -C   10 - fluoroaryl, C   1   -C   10 - alkoxy, C   2   -C   10 - alkenyl, C   7   -C   40 - arylalkyl, C   8   -C   40 - arylalkenyl, or C   7   -C   40 - alkylaryl, or a pair of substituents R   10   , in each case with the atoms connecting them, form a ring, but at least one R   10    is not hydrogen.   
       
     
     
       19. The compound as claimed in  claim 18 , wherein R 10    is C   1    to C   4 - alkyl.   
     
     
       20. The compound as claimed in  claim 18 , wherein R 10    is a hydrogen atom or a C   6   -C   10    aryl group.   
     
     
       21. The compound as claimed in  claim 18 , wherein the substituents R 10    are identical or different and are a hydrogen, C   1   -C   10    alkyl or a C   6   -C   10    aryl.   
     
     
       22. The compound as claimed in  claim 18 , wherein the substituents R 10    are hydrogen and R   5    is ethyl.   
     
     
       23. A compound of the formula
                   
       
         wherein  
           R   3    represents hydrogen; halogen, C   1   -C   10 - alkyl, which is optionally halogenated; C   6   -C   10 - aryl, an —NR   2   15   , —SR   15   , —OSiR   3   15   , —SiR   3   15    or PR   2   15    radical in which R   15    represents halogen, C   1   -C   10 - alkyl or C   6   -C   10 - aryl;    
         
           R 
           5  
           represents any of the radicals defined for R 
           3 
           , except that R 
           5  
           is not hydrogen; and  
         
           R   10    are identical or different and are a hydrogen atom, a halogen atom, a C   2   -C   10 - alkyl group, a C   10 - aryl group, C   1   -C   10 - fluoroalkyl, C   6   -C   10 - fluoroaryl, C   1   -C   10 - alkoxy, C   2   -C   10 - alkenyl, C   7   -C   40 - arylalkyl, C   8   -C   40 - arylalkenyl, or C   7   -C   40 - alkylaryl, or a pair of substituents R   10   , in each case with the atoms connecting them, form a ring, but at least one R   10    is not hydrogen.   
       
     
     
       24. A compound of the formula
                   
       
         wherein 
           R   3    represents hydrogen; halogen, C   1   -C   10 - alkyl, which is optionally halogenated; C   6   -C   10 - aryl, an —NR   2   15   , —SR   15   , —OSiR   3   15   , —SiR   3   15    or PR   2   15    radical in which R   15    represents halogen, C   1   -C   10 - alkyl or C   6   -C   10 - aryl;    
           R   5    is 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, and    
           R   10    are identical or different and are hydrogen, halogen, C   1   -C   10 - alkyl, C   1   -C   10 - fluoroalkyl, C   10 - aryl, C   6   -C   10 - fluoroaryl, C   1   -C   10 - alkoxy, C   2   -C   10 - alkenyl, C   7   -C   40 - arylalkyl, C   8   -C   40 - arylalkenyl, or C   7   -C   40 - alkylaryl, or a pair of substituents R   10   , in each case with the atoms connecting them, form a ring, but at least one R   10    is not hydrogen.   
       
     
     
       25. A compound of the formula
                   
       
         wherein  
           R   3    represents hydrogen; halogen, C   1   -C   10 - alkyl, which is optionally halogenated; C   6   -C   10 - aryl, an —NR   2   15   , —SR   15   , —OSiR   3   15   , —SiR   3   15    or PR   2   15    radical in which R   15    represents halogen, C   1   -C   10 - alkyl or C   6   -C   10 - aryl;    
           R   5    is a halogen atom, a C   1   -C   10 - alkyl group which is optionally halogenated, a 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, and    
           R   10    are identical or different and are hydrogen, halogen, C   2   -C   10 - alkyl, C   1   -C   10 - fluoroalkyl, C   6   -C   10 - aryl, C   6   -C   10 - fluoroaryl, C   1   -C   10 - alkoxy, C   2   -C   10 - alkenyl, C   7   -C   40 - arylalkyl, C   8   -C   40 - arylalkenyl, or C   7   -C   40 - alkylaryl, or a pair of substituents R   10   , in each case with the atoms connecting them, form a ring but at least one R   10    is not hydrogen.   
       
     
     
       26. The compound as claimed in  claim 23 , wherein R 10    is a C   4   -C   10 - alkyl.   
     
     
       27. The compound as claimed in  claim 25 , wherein R 10    is a C   4   -C   10 - alkyl.