Catalyst composition, method of polymerization, and polymer therefrom

Abstract

Catalyst compositions and methods, useful in polymerization processes, utilizing at least two metal compounds are disclosed. At least one of the metal compounds is a Group 15 containing metal compound and the other metal compound is preferably a bulky ligand metallocene-type catalyst. The invention also discloses a new polyolefin, generally polyethylene, particularly a multimodal polymer and more specifically, a bimodal polymer, and its use in various end-use applications such as film, molding and pipe.

1. A process for polymerizing olefin(s) comprising, combining said olefin( s ) ,  a catalyst composition having a first catalyst system  component comprising a Group 15 containing bidentate or  tridentate ligated Group 3 to 7 metal compound wherein the Group 3 to 7 metal atom is bound to at least one leaving group and to at least two  three Group 15 atoms, and wherein at least one of the at least  two of the Group 15 atoms is bound to a Group 15 or 16 atom  are each bound to the third Group  15  atom through a bridging group; and a second catalyst system  component,
   wherein said second catalyst component is a metallocene compound;    
   wherein said first catalyst component and said second catalyst component are added to a polymerization reactor in one of a solution, a suspension or an emulsion;    
   wherein the polymerization process is a continuous gas or slurry phase process, and    
   wherein the Group  15  containing tridentate ligand Group  3  to  7  metal compound is represented by the formula:                      
 wherein R 8    to R   12    are each independently a methyl, ethyl, propyl, or butyl group .  
 
     
     
       2. The process of  claim 1  wherein the second catalyst system comprises a bulky ligand metallocene compound, a conventional transition metal catalyst selected from the group consisting of Ziegler-Natta catalysts, vanadium containing catalysts, and Phillips catalysts, or combinations thereof. 
     
     
       3. The process of  claim 1  wherein the metal in the Group 15 containing metal compound is a Group 4 to 6 metal. 
     
     
       4. The process of  claim 1  wherein the bridging group is selected from the group consisting of a C 1  to C 20  hydrocarbon group, a heteroatom containing group, silicon, germanium, tin, lead, and phosphorus. 
     
     
       5. The process of  claim 1  wherein the Group 15 or 16 atom may also be bound to nothing, a hydrogen, a Group 14 atom containing group, a halogen, or a heteroatom containing group, and wherein each of the two Group 15 atoms are also bound to a cyclic group and may optionally be bound to hydrogen, a halogen, a heteroatom, a hydrocarbyl group, or a heteroatom containing group. 
     
     
       6. The process of  claim 1  wherein the Group 15 containing metal compound is represented by the formula: 
                   
       wherein
 M is a Group 3 to 14 metal,  
 each X is independently a leaving group  
 y is 0 or 1,  
 n is the oxidation state of M,  
 m is the formal charge of Y, Z and L or of Y, Z and L′,  
 L is a Group 15 or 16 element,  
 L′ is a Group 15 or 16 element or Group 14 containing group,  
 Y is a Group 15 element,  
 Z is a Group 15 element,  
 R 1  and R 2  are independently a C 1  to C 20  hydrocarbon group, a heteroatom containing group having up to twenty carbon atoms, silicon, germanium, tin, lead, or phosphorus,  
 R 3  is absent, a hydrocarbon group, hydrogen, a halogen, or a heteroatom containing group,  
 R 4  and R 5  are independently an alkyl group, an aryl group, a substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic aralkyl group, a substituted cyclic aralkyl group or a multiple ring system,  
 R 1  and R 2  may be interconnected to each other, and/or R 4  and R 5  may be interconnected to each other,  
 R 6  and R 7  are independently absent, hydrogen, an alkyl group, halogen, heteroatom or a hydrocarbyl group, and  
 R* is absent, hydrogen, a Group 14 atom containing group, a halogen, or a heteroatom containing group.  
 
     
     
       7. The process of  claim 6  wherein R 4  and R 5  are represented by the formula 
                   
       wherein R 8  to R 12  are each independently hydrogen, a C 1  to C 40  alkyl group, a halide, a heteroatom, or a heteroatom containing group containing up to 40 carbon atoms, wherein any two R groups may form a cyclic group and/or a heterocyclic group, and wherein the cyclic groups may be aromatic. 
     
     
       8. The process of  claim 7  wherein R 9 , R 10  and R 12  are independendy a methyl, ethyl, propyl or butyl group. 
     
     
       9. The process of  claim 8  wherein R 9 , R 10  and R 12  are methyl groups, and R 8  and R 11  are hydrogen. 
     
     
       10. The process of  claim 9  wherein M is a Group 4 metal L, Y, and Z are nitrogen, R 1  and R 2  are a hydrocarbon radical, R 3  is hydrogen, and R 6  and R 7  are absent. 
     
     
       11. The process of  claim 9  wherein M is a Group 4 metal, L and Z are nitrogen, L′ is a hydrocarbyl radical, and R 6  and R 7  are absent. 
     
     
       12. The process of claim  2    1  wherein the second catalyst system  component comprises a bulky ligand  metallocene compound of the general formula L D MQ 2 (YZ)X n 
   L A   L   B   MQ   n  or  L   A   AL   B   MQ   n   
 wherein M is a Group 3 to 16 metal   4 ,  5  or  6  metal atom,  
 L D  is a bulky ligand that is bonded to M, 
 L A    and L   B    are selected from the group consisting of cyclopentadienyl, tetrahydroindenyl, indenyl, fluorenyl, and substituted versions thereof, L   A    and L   B    are each bonded to M;   
 Q is a univalent anionic ligand bonded to M  monoanionic leaving group,  
 Q 2 (YZ) forms a unicharged polydentate ligand, 
 X is a univalent anionic group or a divalent anionic group, and 
 n is 1 or 2 
 A is a divalent bridging group containing at least one Group  13  to Group  16  atom; and  
   n is  0 ,  1  or  2   .  
 
     
     
       13. The process of  claim 12  wherein X is a carbamate, carboxylate, or other heteroallyl moiety described by the unicharged polydentate ligand Q 2 (YZ). 
     
     
       14. The process of  claim 12  wherein M is a Group 4 to 6 metal. 
     
     
       15. The process of  claim 12  wherein M is a Group 4 metal and L D  is an indenyl group or a fluorenyl group . 
     
     
       16. The process of  claim 1  wherein the second catalyst system comprises a conventional transition metal catalyst selected from the group consisting of Ziegler-Natta catalysts, vanadium containing catalysts, Phillips catalysts and combinations thereof. 
     
     
       17. The process of  claim 1  wherein the catalyst systems comprise  composition further comprises an activator. 
     
     
       18. The process of  claim 1  wherein the polymerization process is a continuous gas or slurry phase process. 
     
     
       19. The process of  claim 1  wherein the olefin(s) are ethylene and one or more other olefin(s). 
     
     
       20. The process of claim  2  wherein the Group 15 containing bidentate or tridentate ligated Group 3 to 7 metal compound and the bulky ligand metallocene compound   1  wherein said first catalyst component and said second catalyst component are present in a molar ratio of 1:99 to 99:1. 
     
     
       21. The process of claim  2  wherein the Group 15 containing bidentate or tridentate ligated Group 3 to 7 metal compound and the bulky ligand metallocene compound   1  wherein said first catalyst component and said second catalyst component are present in a molar ratio of 20:80 to 80:20.