Process for polymerizing olefins with non-metallocene catalysts

Abstract

Nonmetallocenes, process for preparing them and their use for the polymerization of olefins. The present invention describes a novel group of specific transition metal compounds, referred to as nornmetallocene compounds, and catalyst systems prepared therefrom. These catalyst systems which have become obtainable for the first time are suitable for the polymerization of olefins.

1 . A process for polymerizing one or more olefins of the formula R m —CH═CH—R n  where R m  and R n  are identical or different and are each a hydrogen atom or an organic radical having from 1 to 20 carbon atoms, and R m  and R n  together with the atoms connecting them may form one or more rings, comprising polymerizing said olefin or olefins in the presence of a catalyst system comprising a compound of the formula I  
       
         
           
           
               
               
           
         
       
       where 
 M 1  is a metal of groups III to XII of the Periodic Table of the Elements and  
 D 1  are identical or different and are each a donor atom of group XV or XVI of the Periodic Table of the Elements and  
 D 2  are identical or different and are each a donor atom of group XV of XVI of the Periodic Table of The Elements and  
 Z is a bridging structural element between the two donor atoms D 1  and  
 X are identical or different and are each a hydrogen atom, a C 1 -C 10 -hydrocarbon group or a halogen atom or OR 6 , SR 6 , OSO 2 R 6 , OSi(R 6 ) 3 , Si( 6 ) 3 , P(R 6 ) 2 , P(R 6 ) 3 , NCR 6 , N(R 6 ) 3 , B(R 6 ) 4 , substituted or unsubstituted pyridine or N(R 6 ) 2 , and  
 R 1  are identical or different and are each a hydrogen atom, a C 1 -C 20 -alkyl group, a C 6 -C 20 -aryl group, a C 7 -C 20 -alkylaryl group, a C 7 -C 30 -arylalkyl group, a C 2 -C 20 -alkenyl group, a C 2 -C 20 -alkynyl group or a halogen-containing C 1 -C 20 -alkyl group, C 6 -C 20 -aryl group, C 7 -C 20 -alkylaryl group, C 7 -C 30 -arylalkyl group, C 2 -C 20 -alkenyl group, C 2 -C 20 -alkynyl group or a heteroatom-containing C 1 -C 20 -alkyl group, C 6 -C 20 -aryl group, C 7 -C 20 -alkylaryl group, C 7 -C 30 -arylalkyl group, C 2 -C 20 -alkenyl group, C 2 -C 20 -alkynyl group or Si(R 6 ) 3 , where one or more radicals R 1  together with one or more radicals R 2  may form a monocyclic or polycyclic ring system, which may in turn be substituted by one or more radicals R 6 , and  
 R 2  are identical or different and are each a hydrogen atom, a C 1 -C 20 -alkyl group, a C 6 -C 20 -aryl group, a C 7 -C 20 -alkylaryl group, a C 7 -C 30 -arylalkyl group, a C 2 -C 20 -alkenyl group, a C 2 -C 20 -alkynyl group or a halogen-containing C 1 -C 20 -alkyl group, C 6 -C 20 -aryl group, C 7 -C 20 -alkylaryl group, C 7 -C 30 -arylalkyl group, C 2 -C 20 -alkenyl group, C 2 -C 20 -alkynyl group or a heteroatom-containing C 1 -C 20 -alkyl group, C 6 -C 20 -aryl group, C 7 -C 20 -alkylaryl group, C 7 -C 30 -arylalkyl group, C 2 -C 20 -alkenyl group, C 2 -C 20 -alkynyl group or Si(R 6 ) 3 , where one or more radicals R 2  together with one or more radicals R 1  and/or R 3  may form a monocyclic or polycyclic ring system, which may in turn be substituted by one or more radicals R 6 , and  
 R 3  are identical or different and are each a hydrogen atom, a C 1 -C 20 -alkyl group, a C 6 -C 20 -aryl group, a C 7 -C 20 -alkylaryl group, a C 7 -C 30 -arylalkyl group, a C 2 -C 20 -alkenyl group, a C 2 -C 20  alkynyl group or a halogen-containing C 1 -C 20 -alkyl group, C 6 -C 20 -aryl group, C 7 -C 20 -alkylaryl group, C 7 -C 30 -arylalkyl group, C 2 -C 20 -alkenyl group, C 2 -C 20 -alkynyl group or a heteroatom-containing C 1 -C 20 -alkyl group, C 6 -C 20 -aryl group, C 7 -C 20 -alkylaryl group, C 7 -C 30 -arylalkyl group, C 2 -C 20 -alkenyl group, C 2 -C 20 -alkynyl group or Si(R 6 ) 3 , where one or more radicals R 3  together with one or more radicals R 2  may form a monocyclic or polycyclic ring system, which may in turn be substituted by one or more radicals R 6 , and  
 R 4  are identical or different and are each a hydrogen atom, a C 1 -C 20 -alkyl group, a C 6 -C 20 -aryl group, a C 7 -C 20 -alkylaryl group, a C 7 -C 30 -arylalkyl group, a C 2 -C 20 -alkenyl group, a C 2 -C 20 -alkynyl group or a halogen-containing C 1 -C 20 -alkyl group, C 6 -C 20 -aryl group, C 7 -C 20 -alkylaryl group, C 7 -C 30 -arylalkyl group, C 2 -C 20 -alkenyl group, C 2 -C 20 -alkynyl group or a heteroatom-containing C 1 -C 20 -alkyl group, C 6 -C 20 -aryl group, C 7 -C 20 -alkylaryl group, C 7 -C 30 -arylalkyl group, C 2 -C 20 -alkenyl group or C 2 -C 20 -alkynyl group, and  
 R 5  are identical or different and are each a hydrogen atom, a C 1 -C 20 -alkyl group, a C 6 -C 20 -aryl group, a C 7 -C 20 -alkylaryl group, a C 7 -C 30 -arylalkyl group, a C 2 -C 20 -alkenyl group, a C 2 -C 20 -alkynyl group or a halogen-containing C-C 20 -alkyl group, C 6 -C 20 -aryl group, C 7 -C 20 -alkylaryl group, C 7 -C 30 -arylalkyl group, C 2 -C 20 -alkenyl group, C 2 -C 20 -alkynyl group or a heteroatom-containing C 1 -C 20 -alkyl group, C 6 -C 20 -aryl group, C 7 -C 20 -alkylaryl group, C 7 -C 30 -arylalkyl group, C 2 -C 20 -alkenyl group, C 2 -C 20 -alkynyl group, where a plurality of radicals R 5  may together form a monocyclic or polycyclic ring system, and  
 R 6  are identical or different and are each a hydrogen atom, a halogen atom, a C 1 -C 10 -alkyl group, a C 6 -C 20 -aryl group, a C 7 -C 20 -alkylaryl group, a C 7 -C 30 -arylalkyl group, a C 2 -C 20 -alkenyl group, a C 2 -C 20 -alkynyl group or a halogen-containing C 1 -C 20 -alkyl group, C 6 -C 20 -aryl group, C 7 -C 20 -alkylaryl group, C 7 -C 30 -arylalkyl group, C 2 -C 20 -alkenyl group, C 2 -C 20 -alkynyl group or a heteroatom-containing C 1 -C 20 -alkyl group, C 6 -C 20 -aryl group, C 7 -C 20 -alkylaryl group, C 7 -C 30 -arylalkyl group, C 2 -C 20 -alkenyl group, C 2 -C 20 -alkynyl group, and  
 a are identical or different and are each an integer from 1 to 10 and  
 b are identical or different and are each an integer from 0 to 3 and  
 c are identical or different and are each an integer from 0 to 2 and  
 d are identical or different and are each an integer from 0 to 2 and  
 e are identical or different and are each an integer from 0 to 2 and  
 f are identical or different and are each an integer from 2 to 20 and  
 g are identical or different and are each 1 or 2 and  
 h are identical or different and are each an integer from 1 to 4 and  
 i are identical or different and are each an integer from 0 to 24 and  
 j are identical or different and are each an integer from 0 to 10,  
 with the proviso that complexes in which Za(R 5 ) f  is unsubstituted or substituted ethyl and D 1  is nitrogen, R 3  is hydrogen, d is 1 and two R 2  together form a substituted benzene ring which is substituted by D 2 =O excluded.  
 
     
     
         2 . The process of  claim 1 , wherein 
 M 1  is selected from the group consisting of Sc, Y, La, Ti, Zr, Hf, V, Cr, Mo, Mn, Fe, Ru, Co, Rh, Ni, Pd, and Cu and    D 1  are identical or different and are each selected from the group consisting of N, P, As, O, S, Se, and Te and    D 2  are identical or different and are each selected from the group consisting of N, P, As, O, S, Se, and te.    
     
     
         3 . The process of  claim 1 , wherein 
 D 1 -Z 1 (R 5 ) f D 1  is a structure selected from the group consisting of IIa to IIz                                                              where D 1 m R 6  and i are as defined in  claim 1 .    
     
     
         4 . The process of  claim 1 , wherein 
 a are identical or different and are each an integer from 1 to 4 and    b are identical or different and are each an integer from 0 to 2 and    c are identical or different and are each an integer from 0 to 2 and    d are identical or different and are each an integer from 0 to 2 and    e are identical or different and are each an integer from 0 to 2 and    f are identical or different and are each an integer from 2 to 20 and    g are identical or different and are each 1 or 2 and    h are identical or different and are each an integer from 1 to 4 and    i are identical or different and are each an integer from 0 to 24 and    j are identical or different and are each an integer from 0 to 10.    
     
     
         5 . The process of  claim 3 , wherein 
 M 1  is selected from the group consisting of Ti, Zr, Hf, Fe, Co, Ni, and Pd and    D 1  are identical or different and are each selected from the group consisting of N, P, O, and S, and    D 2  are identical or different and are each selected from the group consisting of N, P, O, and S, and    Z corresponds to one of the formulae II d, II j, II o, II r or II s and    X are identical or different and are-each selected from the group consisting of chloride, bromide, iodide, methyl, ethyl, propyl, ethenyl, propynyl, phenyl, benzyl, methoxy, trifluoromethanesulfonyl, dimethylamido, tetrafluoroborate, triphenylphosphine, acetonitrile, trimethylsilyl, and pyridine, and    R 1  are identical or different and are each a selected from the group consisting of hydrogen, methyl, ethyl, propyl, i-propyl, tert-butyl, phenyl, benzyl, trimethylsilyl, and tert-butyldimethylsilyl, or a radical R 1  together with a radical R 2  forms a monocyclic or polycyclic ring system, which may in turn be substituted by one or more radicals R 6 , and    R 2  are identical or different and are each a selected from the group consisting of hydrogen, methyl, ethyl, propyl, i-propyl, tert-butyl, phenyl, benzyl, trimethylsilyl, and tert-butyldimethylsilyl, or a radical R 2  together with a radical R 1  forms a monocyclic or polycyclic ring system, which may in turn be substituted by one or more radicals R 6 , and    R 3  are identical or different and are each a selected from the group consisting of hydrogen, methyl, ethyl, propyl, i-propyl, tert-butyl, phenyl, benzyl, trimethylsilyl, and tert-butyldimethylsilyl, and    R 4  are identical or different and are each a selected from the group consisting of hydrogen, methyl, ethyl, propyl, i-propyl, tert-butyl, phenyl, benzyl, trimethylsilyl, and tert-butyldimethylsilyl, and    R 5  are identical or different and are each a selected from the group consisting of hydrogen, methyl, ethyl, propyl, i-propyl, tert-butyl, phenyl, benzyl, trimethylsilyl, and tert-butyldimethylsilyl, or a plurality of radicals R 5  may together form a monocyclic or polycyclic ring system, and    R 6  are identical or different and are each a selected from the group consisting of hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, i-propyl, tert-butyl, phenyl, benzyl, trimethylsilyl, and tert-butyldimethylsilyl, and    a are identical or different and are each 1 or 2 and    b are identical or different and are each an integer from 0 to 2 and    c are identical or different and are each an integer from 0 to 2 and    d are identical or different and are each an integer from 0 to 2 and    e are identical or different and are each O, or I and    f are identical or different and are each an integer from 2 to 20 and    g are identical or different and are each 1 or 2 and    h are identical or different and are each an integer from 1 to 4 and    i are identical or different and are each an integer from 0 to 18 and    j are identical or different and are each an integer from 0 to 6.    
     
     
         6 .- 14 . (canceled)  
     
     
         15 . The process of  claim 1 , wherein M 1  is selected from the group consisting of Sc, Y, La, Ti, Zr, Hf, V, Cr, Mo, Mn, Fe, Ru, Co, Rh, Ni, Pd, and Cu.  
     
     
         16 . The process of  claim 1 , wherein D 1  is a donor atom of the group consisting of N, P, As, O, S, Se, and Te.  
     
     
         17 . The process of  claim 1 , wherein D 2  is a donor atom of the group consisting of N, P, As, O, S, Se, and Te.  
     
     
         18 . The process of  claim 1 , wherein X is a C 1 -C 10  hydrocarbon selected from the group consisting of C 1 -C 10 -alkyl, C 6 -C 10 -aryl, C 7 -C 20 -alkylaryl, C 7 -C 20 -arylalkyl, C 2 -C 20 -alkenyl, and C 2 -C 20 -alkynyl.  
     
     
         19 . The process of  claim 1 , wherein at least one of R m  and R n  is an organic radial having from 1 to 10 carbon atoms.