Complexes of pyridyldiimines with vanadium and other transition metals, and their use as olefin oligomerization and polymerization catalysts

Abstract

Pyridyldiimine ligands having one of the following structures: and pyridyldiimine metal complexes having one of the following structures: for example the Group 4b, 5b, 6b, 7b, and 8 transition metal (M) complexes such as vanadium complexes, are disclosed. The invention also relates to the use of these metal complexes as olefin polymerization or oligomerization catalysts, optionally in combination with metal alumoxane and similar catalyst activators. Certain of these catalysts have been found to possess robust activity as selective oligomerization catalysts, while others of these catalysts act selectively as polymerization catalysts. A method of synthesizing the above-noted ligands using p-toluenesulfonic acid as a catalyst is also disclosed.

That which is claimed is:  
     
         1 . A ligand having one of the following structures:  
       
         
           
           
               
               
           
         
       
       wherein: 
 R 1 -R 22  are independently selected from halogen; nitrile; straight or branched chain alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, or alkaryl moieties or combinations thereof, any of which optionally include substituent or linking heteroatoms of halogen, oxygen, nitrogen, silicon, phosphorus, or sulfur; but excluding the species in which: 
 R 1 , R 5 , R 6 , and R 10  are isopropyl; R 11 -R 12  are methyl; and R 2 -R 4 , R 7 -R 9 , and R 13 -R 15  are hydrogen;  
 R 3  and R 8  are —CF 3 ; R 11  and R 12  are methyl; and R 1 -R 2 , R 4 -R 7 , R 9 -R 10 , and R 13 -R 15  are hydrogen;  
 R 1 , R 5 , R 6 , and R 10 -R 12  are methyl; R 2 -R 4 , R 7 -R 9 , and R 13 -R 15  are hydrogen;  
 R 1 , R 3 , R 5 , R 6 , R 8  and R 10 -R 12  are methyl; R 2 , R 4 , R 7 , R 9 , and R 13 -R 15  are hydrogen;  
 R 1 , R 3 , R 6 , R 8 , R 11 , and R 12  are methyl; R 2 , R 4 , R 5 , R 7 , R 9 , R 10 , and R 13 -R 15  are hydrogen;  
 R 1 , R 5 , R 6 , and R 10  are methyl; R 2 -R 4 , R 7 -R 9 , and R 11 -R 15  are hydrogen.  
 R 1 , R 5 , R 6 , and R 10  are isopropyl; R 11  and R 12  are methyl; and R 2 -R 4 , R 7 -R 9 , and R 13 -R 15  are hydrogen;  
 R 1 , R 5 , R 6 , R 10 -R 12  are methyl; and R 2 -R 4 , R 7 -R 9 , and R 13 -R 15  are hydrogen; and  
 R 1  and R 6  are t-butyl; R 11 -R 12  are methyl; and R 2 -R 5 , R 7 -R 10 , and R 13 -R 15  are hydrogen.  
 R 1 -R 10  and R 13 -R 15  are hydrogen and R 11 -R 12  are methyl  
 R 3  and R 8  are methoxy moieties; R 11 -R 12  is methyl, and R 1 -R 2 , R 4 -R 7 , R 9 -R 10 , and R 13 -R 15  are hydrogen;  
 R 16  and R 17  are benzyl moieties, R 18  and R 19  are methyl moieties, and R 20 -R 22  are hydrogens;  
 R 1 , R 6 , R 11  and R 12  are methyl and R 2 -R 5 , R 7 -R 10 , and R 13 -R 15  are hydrogen;  
 R 1 , and R 6  are ethyl; R 11  and R 12  are methyl; and R 2 -R 5 , R 7 -R 10 , and R 13 -R 15  are hydrogen; and  
 R 1  and R 6  are isopropyl; R 11  and R 12  are methyl; and R 2 -R 5 , R 7 -R 10 , and R 13 -R 15  are hydrogen.  
 
 
     
     
         2 . A metal-ligand complex having one of the following structures:  
       
         
           
           
               
               
           
         
       
       wherein: 
 R 1 -R 22  are independently selected from halogen; nitrile; straight or branched chain alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, or alkaryl moieties or combinations thereof, any of which optionally include substituent or linking heteroatoms of halogen, oxygen, nitrogen, silicon, phosphorus, or sulfur;  
 M is a metal selected from Group 4b, 5b, and 6b transition metals;  
 X is an anion; and  
 n is 2, 3, 4, 5, or 6.  
 
     
     
         3 . A composition comprising: 
 a. a metal-ligand complex having one of the following structures:                          wherein:    R 1 -R 22  are independently selected from halogen; nitrile; straight or branched chain alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, or alkaryl moieties or combinations thereof, any of which optionally include substituent or linking heteroatoms of halogen, oxygen, nitrogen, silicon, phosphorus, or sulfur;    M is a metal selected from Group 4b, 5b, and 6b transition metals;    X is an anion; and    n is 2, 3, 4, 5, or 6; and 
 b. an amount of a methylaluminoxane effective to activate said metal-ligand complex for use as an olefin oligomerization or polymerization catalyst.  
   
     
     
         4 . An oligomerization process comprising contacting under oligomerization conditions in a reaction zone: 
 a. at least one olefin; and    b. at least one catalyst having one of the following structures:                          wherein:    R 1 -R 22  are independently selected from halogen; nitrile; straight or branced chain alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, or alkaryl moieties or combinations thereof, any of which optionally include substituent or linking heteroatoms of halogen, oxygen, nitrogen, silicon, phosphorus, or sulfur;    M is a metal selected from Group 4b, 5b, and 6b transition metals;    X is an anion; and    n is 2, 3, 4, 5, or 6.    
     
     
         5 . A polymerization process comprising: contacting under polymerizing conditions in a reaction zone: 
 a. at least one olefin; and    b. at least one catalyst having one of the following structures:                          wherein:    R 1 -R 22  are independently selected from halogen; nitrile or isonitrile; cyanate or isocyanate; straight or branched chain alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, or alkaryl moieties or combinations thereof, any of which optionally include substituent or linking heteroatoms of halogen, oxygen, nitrogen, silicon, phosphorus, or sulfur;    M is a metal selected from Group 4b, 5b, and 6b transition metals,    X is an anion; and    n is 2, 3, 4, 5, or 6.    
     
     
         6 . A method of forming the pyridyldiimine ligands of generic structure I in  claim 1 , comprising: 
 a. providing as a starting material                        wherein R 11 -R 15  are independently defined as in  claim 1;       b. providing a starting material comprising at least one compound having the structure:                        wherein R 1 -R 5  for each compound of Structure IV are independently defined as in  claim 1;  and      c. reacting said starting materials in the presence of a catalytic amount of para-toluenesulfonic acid.    
     
     
         7 . The product produced by the process of  claim 4 , having a 1-hexene purity of at least about 80%.