Polymerization catalyst systems, their use, their products and articles thereof

Abstract

The present invention relates to a process for the polymerization of monomers utilizing a bulky ligand hafnium transition metal metallocene-type catalyst compound, to the catalyst compound itself and to the catalyst compound in combination with an activator. The invention is also directed to an ethylene copolymer composition produced by using the bulky ligand hafnium metallocene-type catalyst of the invention, in particular a single reactor polymerization process.

What is claimed is:  
     
         1 . A catalyst system comprising a bulky ligand hafnium transition metal metallocene-type catalyst compound represented by the formula: 
       (C 5 H 5-d-f R″ d ) e R′″ f HfQ 4−e   
       wherein (C 5 H 5-d-f R″ d ) is a substituted cyclopentadienyl ligand bonded to Hf; wherein at least one (C 5 H 5-d-f R″ d ) is substituted with at least one R″, wherein said R″ is selected from one or more of n-propyl, isopropyl, n-butyl, isobutyl, or n-pentyl, each additional R″, which can be the same or different is hydrogen or a substituted or unsubstituted hydrocarbyl having from 1 to 30 carbon atoms or combinations thereof where two or more carbon atoms are not joined together to form a part of a substituted or unsubstituted ring or ring system, R′″ is one or more or a combination of the group consisting of carbon, germanium, silicon, phosphorous and nitrogen atoms containing radical bridging two (C 5 H 5-d-f R″ d ) rings, or bridging one (C 5 H 5-d-f R″ d ) ring to Hf; each Q which can be the same or different is selected from the group consisting of a hydride, substituted and unsubstituted hydrocarbyl having from 1 to 30 carbon atoms, halogen, alkoxides, aryloxides, amides, phosphides and combination thereof; two Q's together form an alkylidene ligand or cyclometallated hydrocarbyl ligand or other divalent anionic chelating ligand; d is 1, 2, 3, or 4, f is 1 and e is 1, 2 or 3.  
     
     
         2 . The catalyst system of  claim 1 , wherein e is 2.  
     
     
         3 . A catalyst system comprising a bulky ligand hafnium transition metal metallocene-type catalyst compound represented by the formula: 
       (C 5 H 5-d-f R″ d ) e R′″ f HfQ 4−e   
       wherein (C 5 H 5-d-f R″ d ) is a substituted cyclopentadienyl ligand bonded to Hf, wherein at least one (C 5 H 5-d-f R″ d ) is substituted with R″, and R″ consists essentially of one of n-propyl, n-butyl, isobutyl, or isopropyl, each additional R″, which can be the same or different is hydrogen or a substituted or unsubstituted hydrocarbyl having from 1 to 30 carbon atoms or combinations thereof where two or more carbon atoms are not joined together to form a part of a substituted or unsubstituted ring or ring system, R′″ is one or more or a combination of the group consisting of carbon, germanium, silicon, phosphorous and nitrogen atoms containing radical bridging two (C 5 H 5-d-f R″ d ) rings, or bridging one (C 5 H 5-d-f R″ d ) ring to Hf; each Q which can be the same or different is selected from the group consisting of a hydride, substituted and unsubstituted hydrocarbyl having from 1 to 30 carbon atoms, halogen, alkoxides, aryloxides, amides, phosphides and combination thereof; two Q's together form an alkylidene ligand or cyclometallated hydrocarbyl ligand or other divalent anionic chelating ligand; d is 1, 2, 3, or 4, f is 1 and e is 1, 2 or 3.