Method for producting fulvene metal complexes

Abstract

The invention relates to a process for the preparation of polyolefins by polymerizing olefins of the formula CH 2 CHR in which R=H or C 1 -C 10 alkyl, on their own or as a mixture, if appropriate together with C 4 -C 12 α,ω-diolefins, in solvents, liquid monomers or the gas phase, at temperatures between −50° and 200° C., using a catalyst system composed of a soluble, halogen-containing transition metal compound of the general formula (cyclopentadienyl) 2 Me R Hal in which R is cyclopentadienyl or a C 1 -C 6 alkyl radical or a halogen, in particular chlorine, Me is a transition metal, in particular zirconium, and Hal is a halogen, in particular chlorine, and a compound, containing aluminum, of the aluminoxane type having the general formulae Al 2 OR 4 (Al(R)—O) n for a linear aluminoxane and/or (Al(R)—O) n—2 for a cyclic aluminoxane, in which n is a number from 4 to 20 and R is a methyl or ethyl radical, preferably a methyl radical.

1 . Process for the preparation of fulvene-metal complexes of the formula (Ia)  
       
         
           
           
               
               
           
         
         or of the formula (Ib)  
         
           
             
             
                 
                 
             
           
         
         wherein  
         M is a metal from group IIIb, IVb, Vb or VIb or the lanthanides or the actinides of the periodic table of the elements according to IUPAC,  
         A denotes an anionic ligand optionally with one or more bridges,  
         X denotes a hydrogen atom, a C 1 - to C 10 -alkyl group, a C 1 - to C 10 -alkoxy group, a C 6 - to C 10 -aryl group, a C 6 - to C 10 -aryloxy group, a C 2 - to C 10 -alkenyl group, a C 7 - to C 40 -arylalkyl group, a C 7 -to C 40 -alkylaryl group, a C 8 - to C 40 -arylalkenyl group, a silyl group substituted by C 1 - to C 10 -hydrocarbon radicals, a halogen atom or an amide of the formula NR 7   2 ,  
         L denotes a neutral ligand,  
         R 1 , R 2 , R 3 , R 4 , R 5 , R 6  are identical or different and represent hydrogen, halogen, a cyano group, a C 1 - to C 20 -alkyl group, a C 1 - to C 10 -fluoroalkyl group, a C 6 - to C 10 -fluoroaryl group, a C 1 - to C 10 -alkoxy group, a C 6 - to C 20 -aryl group, a C 6 - to C 10 -aryloxy group, a C 2 - to C 10 -alkenyl group, a C 7 - to C 40 -arylalkyl group, a C 7 - to C 40 -alkylaryl group, a C 8 - to C 40 -arylalkenyl group, a C 2 - to C 10 -alkinyl group, a silyl group substituted by C 1 -C 10 -hydrocarbon radicals, a sulfide group substituted by a C 1 -C 10 -hydrocarbon radical or an amino group which is optionally substituted by C 1 -C 20 -hydrocarbon radicals,  
         or  
         R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , in each case together with the atoms connecting them, form one or more aliphatic or aromatic ring systems, which can contain one or more hetero atoms (O, N, S) and 5 to 10 carbon atoms,  
         R 7  represents hydrogen, a C 1 - to C 20 -alkyl group, a C 6 - to C 20 -aryl group, a C 7 - to C 40 -arylalkyl group, a C 1 - to C 40 -alkylaryl group, a silyl group substituted by C 1 -C 10 -hydrocarbon radicals or an amino group which is optionally substituted by C 1 -C 20 -hydrocarbon radicals,  
         m, p represent the numbers 0, 1, 2, 3 or 4, which result from the valency and the bonding state of M, and  
         k represents the number 1, 2 or 3, and the sum of k+m+p is 1 to 5, depending on the oxidation level of M, and  
         n is a number from 0 to 10,  
         by reaction of a transition metal compound of the formula (IIa) or (IIb)  
         A m X s M (IIa) 
         or  
         A m X s L n M  (IIb) 
         wherein  
         A, X, L, M, m, s and n have the abovementioned meaning and  
         s is 2, 3, 4, 5 or 6 and s is >p,  
         with a fulvene compound of the formula (III)  
         
           
             
             
                 
                 
             
           
         
         wherein  
         R 1 , R 2 , R 3 , R 4 , R 5  and R 6  have the abovementioned meaning,  
         in the presence of a reducing agent.  
       
     
     
         2 . Process according to  claim 1 , characterized in that the reaction is carried out in a suitable reaction medium at temperatures of −100 to +250° C.  
     
     
         3 . Process according to  claim 1 , characterized in that alkali metals, alkaline earth metals or lithium-alkyls are used as the reducing agent.  
     
     
         4 . Process according to  claim 1 , characterized in that the reaction is carried out in a solvent.  
     
     
         5 . Process according to  claim 4 , characterized in that the reaction is carried out in an ether.  
     
     
         6 . Fulvene-metal complexes of the formula (Ia) or (Ib), wherein 
 M is a metal from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum and chromium,    k is 1 and    A, X, L, m, n, p, R 1 , R 2 , R 3 , R 4 , R 5  and R 6  have the abovementioned meaning,    with the exception of the compounds of the formula (Ia) or (Ib) wherein    R 1  and R 2  represent hydrogen and at the same time R 3 , R, R 5  and R 6  represent a methyl group and at the same time A denotes a pentamethylcyclopentadienyl group or a carboranediyl group of the formula C 2 B 9 11 11 .    
     
     
         7 . Catalyst system comprising: 
 (a) a fulvene-metal complex of the formula (Ia) or (Ib) prepared by the process according to  claim 1 , wherein 
 M is a metal from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum and chromium,  
 k is 1 and  
 A, X, L, m, n, p, R 1 , R 2 , R 3 , R 4 , R 5  and R 6  have the abovementioned meaning,  
   and    (b) a cocatalyst suitable for activating the metal complex (a), the molar ratio of component (a) to component (b) being in the range from 1:0.1 to 1:10,000.    
     
     
         8 . Use of the catalyst system according to  claim 7  for the polymerization of olefins and/or dienes.