Polyolefins prepared with metallocene catalysts having 2-substituted indenyl type ligands

Abstract

<DEL-S DATE="20010605" ID="DEL-S-00001">The novel metallocenes of the formula Iin which, preferably, M1 is Zr or Hf, R1 and R2 are alkyl or halogen, R3 and R4 are hydrogen, R5 and R6 are alkyl or haloalkyl, -(CR8R9)m-R7-(CR8R9)n- is a single- or multi-membered chain in which R7 may also be a (substituted) hetero atom, m+n is zero or 1, and R10 is hydrogen, form, together with aluminoxanes as cocatalysts, a very effective catalyst system for the preparation of polyolefins or high stereospecificity and high melting point.<DEL-E ID="DEL-S-00001"> <INS-S DATE="20010605" ID="INS-S-00001">Polyolefins with unique or improved properties are obtained by polymerizing an olefin in the presence of a metallocene combined with a cocatalyst, wherein the metallocene is preferably a zirconocene or a hafnocene, and the Zr or Hf central atom is coordinated with two ligands which are derivatives of 2-substituted indenyl nuclei and which are substituted with at least one and up to four groups (e.g. aliphatic or aromatic groups) on the six-member rings of the indenyl nuclei. The indenyl nuclei are optionally substituted at the 3-position and are joined by a 1,1'-bridge of the formula -(CR8R9)m-R7-(CR8R9)n-, which is a single- or multi-membered chain in which R7 can also be a (substituted) hetero atom, m and n are identical or different and are zero, 1, or 2, and m+n is zero, 1, or 2.<INS-E ID="INS-S-00001">

We claim:  
     
       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 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                    
       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-methyl4,5,6,7-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  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 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 or a C 7 -C 14 -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 polyolefin made by polymerizing an olefin in the presence of a combination comprising a metallocene compound and a cocatalyst, said metallocene compound being 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    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   , —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,  
         
           
           
               
               
           
         
       
       
         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 
         , except that at least one of the R 
         10  
         radicals is not hydrogen. 
       
     
     
       17. The polyolefin as claimed in claim  16 , wherein said combination comprises said metallocene compound of formula I and an aluminoxane.