Polymerization catalyst systems comprising substituted hafnocenes

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 hafnocene comprises at least one cyclopentadienyl ligand including at least one linear or isoalkyl substituent of at least 3 carbon atoms.

1. A gas- phase  process for polymerizing olefin(s), excluding cyclic olefin(s), in the presence of a catalyst system comprising a hafnium metallocene catalyst compound having at least one cyclopentadienyl or cyclopentadienyl derived ligand substituted with at least one linear or iso alkyl group having from 3 to 10 carbon atoms, and an activator  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, 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 or two or more carbon atoms are joined together to form a part of a substituted or unsubstituted ring or ring system having  4  to  30  carbon atoms, 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  0  or  1 , and e is  1 ,  2  or  3 , said catalyst system further comprising an activator and a support, wherein the activator and the hafnium metallocene catalyst compound are premixed in a solvent, and then combined with the support and then dried, to produce a free - flowing powder, and wherein the catalyst has a catalyst productivity of greater than  1000   ( g polymer )/( g catalyst*h* 150  psi )  at  85 ° C.    
     
     
       2. The process in accordance with  claim 1  where the linear or iso alkyl group has 3 to 5 carbon atoms  wherein said hafnium metallocene catalyst compound is one of:
   bis  ( n - propyl cyclopentadienyl )  hafnium dichloride, dimethyl, or dihydride; bis  ( n - pentyl cyclopentadienyl )  hafnium dichloride, or dimethyl;  ( n - propyl cyclopentadienyl )( n - butyl cyclopentadienyl )  hafnium dimethyl or dichloride; bis  (   2   - n - propyl indenyl )  hafnium dichloride or dimethyl; bis  (   1 , 2   - n - propyl, methyl cyclopentadienyl )  hafnium dichloride or dimethyl;  ( n - propyl cyclopentadienyl ) (   1 , 3   - n - propyl, n - butyl cyclopentadienyl )  hafnium dimethyl or dichloride.    
 
     
     
       3. The process in accordance with  claim 1  wherein the ligand is one or more cyclopentadienyl ligands, wherein one of the cyclopentadienyl ligands is substituted with at least one linear or iso alkyl having 3 or 4 carbon atoms. 
     
     
       4. The process in accordance with  claim 1  wherein the ligands are two cyclopentadienyl rings each substituted with at least one linear or iso alkyl group having 3 to 10 carbon atoms. 
     
     
       5. The process in accordance with  claim 2  wherein the linear or iso alkyl group is selected from one or more of the group consisting of n-propyl, isopropyl, n-butyl, isobutyl and n-pentyl. 
     
     
       6. The process in accordance with  claim 1  wherein the olefin(s) are alpha-olefins having from 2 to 12 carbon atoms. 
     
     
       7. The process in accordance with  claim 1  wherein the olefin(s) are ethylene in combination with one or more other alpha-olefin(s) having from 3 to 10 carbon atoms. 
     
     
       8. The process in accordance with  claim 1  wherein the process is a gas phase process. 
     
     
       9. The process in accordance with  claim 1  wherein the catalyst system further comprises a support. 
     
     
       10. The process in accordance with  claim 1  wherein the hafnium metallocene catalyst compound is bis(n-propyl-cyclopentadienyl) hafnium dichloride. 
     
     
       11. A continuous gas phase process for polymerizing olefin(s), excluding cyclic olefin(s), in a fluidized bed gas phase reactor in the presence of a catalyst system to produce a polymer product, the catalyst system comprising an activator and a hafnium metallocene catalyst compound having at least one cyclopentadienyl or cyclopentadienyl derived ligand substituted with at least one linear or iso alkyl group having from 3 to 10 carbon atoms,  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, 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 or two or more carbon atoms are joined together to form a part of a substituted or unsubstituted ring or ring system having  4  to  30  carbon atoms, 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  0  or  1 , and e is  1 ,  2  or  3 , said catalyst system further comprising a support, wherein the activator and the hafnium metallocene catalyst compound are premixed in a solvent, and then combined with the support and then dried, to produce a free - flowing powder, and wherein the catalyst has a catalyst productivity of greater than  1000   ( g polymer )/( g catalyst*h* 150  psi )  at  85 ° C.,  and the polymer product comprising less than 2 ppm hafnium. 
     
     
       12. The process of  claim 11  wherein the polymer product comprises less than 1 ppm hafnium. 
     
     
       13. The process in accordance with  claim 11  wherein the catalyst system is supported  said hafnium metallocene catalyst compound is one of:
   bis  ( n - propyl cyclopentadienyl )  hafnium dichloride, dimethyl, or dihydride; bis  ( n - pentyl cyclopentadienyl )  hafnium dichloride, or dimethyl;  ( n - propyl cyclopentadienyl )( n - butyl cyclopentadienyl )  hafnium dimethyl or dichloride; bis  (   2   - n - propyl indenyl )  hafnium dichloride or dimethyl; bis  (   1 , 2   - n - propyl, methyl cyclopentadienyl )  hafnium dichloride or dimethyl;  ( n - propyl cyclopentadienyl ) (   1 , 3   - n - propyl, n - butyl cyclopentadienyl )  hafnium dimethyl or dichloride.    
 
     
     
       14. The process in accordance with  claim 11  wherein the polymer product has a density greater than 0.915 g/cc. 
     
     
       15. The process in accordance with  claim 11  wherein the olefin(s) are ethylene and at least one alpha-olefin(s) having 3 to 8 carbon atoms. 
     
     
       16. The process in accordance in accordance with  claim 11  wherein the catalyst system is represented by the formula:
   (C 5 H 5-d-f R″ d ) e R′″ f HfQ g-e    
 
       wherein (C 5 H 5-d-f R″ d ) is an unsubstituted or 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″ which is an alkyl group selected from the group consisting of n-propyl, isopropyl, isobutyl and 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, or two or more carbon atoms are joined together to form a part of a substituted or unsubstituted ring or ring system having 4 to 30 carbon atoms, 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; where g is an integer corresponding to the formal oxidation state of Hf, d is 0, 1, 2, 3, 4, or 5, f is 0 or 1 and e is 1, 2, or  3, and  the polymer product has a melt index less than  0.1 dg/min without the addition of hydrogen to the process and wherein the hafnium metallocene catalyst compound is bis( n - propyl - cyclopentadienyl )  hafnium dichloride and said activator is alumoxane.    
     
     
       17. A continuous slurry phase process for polymerizing olefin(s), excluding cyclic olefin(s), in the presence of a catalyst system to produce a polymer product in a liquid polymerization medium, the catalyst system comprising an activator, a support and a hafnium metallocene catalyst compound having at least one cyclopentadienyl or cyclopentadienyl derived ligand substituted with at least one linear or iso alkyl group having from 3 to 10 carbon atoms  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, 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 or two or more carbon atoms are joined together to form a part of a substituted or unsubstituted ring or ring system having  4  to  30  carbon atoms, 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  0  or  1 , and e is  1 ,  2  or  3 , wherein the activator and the hafnium metallocene catalyst compound are premixed in a solvent, and then combined with the support and then dried, to produce a free - flowing powder, and wherein the catalyst has a catalyst productivity of greater than  1000   ( g polymer )/( g catalyst*h* 150  psi )  at  85 ° C. , and the polymer product comprising less than 2 ppm hafnium. 
     
     
       18. The process in accordance with  claim 17  wherein the polymer product comprises less than 1 ppm hafnium and wherein said hafnium metallocene catalyst compound is one of:
   bis  ( n - propyl cyclopentadienyl )  hafnium dichloride, dimethyl, or dihydride; bis  ( n - pentyl cyclopentadienyl )  hafnium dichloride, or dimethyl;  ( n - propyl cyclopentadienyl )( n - butyl cyclopentadienyl )  hafnium dimethyl or dichloride; bis  (   2   - n - propyl indenyl )  hafnium dichloride or dimethyl; bis  (   1 , 2   - n - propyl, methyl cyclopentadienyl )  hafnium dichloride or dimethyl;  ( n - propyl cyclopentadienyl ) (   1 , 3   - n - propyl, n - butyl cyclopentadienyl )  hafnium dimethyl or dichloride.    
 
     
     
       19. The process in accordance with claim  17    18  wherein the density is greater than 0.900 g/cc. 
     
     
       20. The process in accordance with claim  17    19  wherein the olefins are ethylene and at least one alpha-olefin(s) having 3 to 8 carbon atoms. 
     
     
       21. The process in accordance with  claim 17  wherein the catalyst system is represented by the formula:
   (C 5 H 5-d-f R″ d ) e R′″ f HfQ g-e    
 
       wherein (C 5 H 5-d-f R″ d ) is an unsubstituted or 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″ which is a linear or iso alkyl group having from 3 to 10 carbon atoms, 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 or two or more carbon atoms are joined together to form a part of a substituted or unsubstituted ring or ring system having 4 to 30 carbon atoms, 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 hydride, substituted and unsubstituted hydrocarbyl having from 1 to 30 carbon atoms, halogen, alkoxides, aryloxides, amides, phosphides and combinations thereof; two Q's together form an alkylidene ligand or a cyclometallated hydrocarbyl ligand or other divalent anionic chelating ligand; where g is an integer corresponding to the formal oxidation state of Hf, d is 0, 1, 2, 3, 4 or 5, f is 0 or 1 and e is 1, 2 or 3, and the  polymer product has a melt index less than 0.1 dg/min (ASTM D-1238-F or ASTM D-1238-E) without the addition of hydrogen to the process, wherein the hafnium metallocene catalyst compound is bis( n - propyl - cyclopentadienyl )  hafnium dichloride and wherein said activator is alumoxane.    
     
     
       22. The process in accordance with  claim 3  wherein the linear or iso alkyl group has 3 carbon atoms. 
     
     
       23. A continuous process for polymerizing olefin(s), excluding cyclic olefin(s), in the presence of a catalyst system comprising a hafnium transition metal metalloccne  metallocene catalyst having at least one cyclopentadienyl ring substituted with at least one alkyl group selected from group consisting of n-propyl, isopropyl, isobutyl and n-pentyl, and an activator  represented by the formula:
   ( C   5   H   5-d-f   R″   d ) e   R′″   f   HfQ   g-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, 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 or two or more carbon atoms are joined together to form a part of a substituted or unsubstituted ring or ring system having  4  to  30  carbon atoms, 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  0  or  1 , and e is  1 ,  2  or  3 , a support and an activator, wherein the activator and the hafnium metallocene catalyst compound are premixed in a solvent, and then combined with the support and then dried, to produce a free - flowing powder, and wherein the catalyst has a catalyst productivity of greater than  1000   ( g polymer )/( g catalyst*h* 150  psi )  at  85 ° C.    
     
     
       24. A continuous gas phase process for polymerizing olefins, excluding cyclic olefin, in a fluidized bed gas phase reactor in the presence of a catalyst system to produce a polymer product, the catalyst system comprising an activator, a support and a bulky ligand  hafnium transition metal metallocene catalyst represented by the formula:
   (C 5 H 5-d-f R″ d ) e R′″ f HfQ g-e    
 
       wherein (C 5 H 5-d-f R″ d ) is an unsubstituted or 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″ which is an alkyl group selected from the group consisting of n-propyl, isopropyl, isobutyl  and 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, or two or more carbon atoms are joined together to form a part of a substituted or unsubstituted ring or ring system having 4 to 30 carbon atoms, 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 hydride, substituted and unsubstituted hydrocarbyl having from 1 to 30 carbon atoms, halogen, alkoxides, aryloxides, amides, phosphides and combinations thereof; two Q's together form an alkylidene ligand or cyclometallated hydrocarbyl ligand or other divalent anionic chelating ligand; where g is an integer corresponding to the formal oxidation state of Hf, d is 0, 1, 2, 3, 4 or 5, f is 0 or 1 and e is 1, 2 or  3, wherein the activator and the hafnium metallocene catalyst compound are premixed in a solvent, and then combined with the support and then dried, to produce a free - flowing powder, and wherein the catalyst has a catalyst productivity of greater than  1000   ( g polymer )/( g catalyst*h* 150  psi )  at  85 ° C.,  and the polymer product has a melt index less than 10 dg/min (ASTM D-1238-F or ASTM D-1238-E) without the addition of hydrogen to the process. 
     
     
       25. The process in accordance with  claim 1  wherein the hafnium metallocene catalyst compound is a bis-cyclopentadienyl hafnium metallocene compound. 
     
     
       26. The process in accordance with  claim 1  wherein the activator is alumoxane. 
     
     
       27. The process in accordance with claim  4  where in the linear or iso alkyl group has from 3 to 5 carbon atoms   24 , wherein the hafnium metallocene catalyst compound is bis( n - propyl - cyclopentadienyl )  hafnium dichloride and said activator is alumoxane.    
     
     
       28. The process in accordance with  claim 1  wherein the linear or iso alkyl group has 3 carbon atoms. 
     
     
       29. A continuous gas- phase process for polymerizing olefins, excluding cyclic olefin ( s ) , comprising: combining a )  one or more of ethylene, propylene, butene -   1 , pentene -   1 ,  4   - methyl -   1   - pentene, hexene -   1  and octene -   1  b )  a catalyst comprising a bis n - propyl cyclopentadienyl hafnium dichloride, an activator selected from the group consisting of alumoxane, methyl alumoxane, modified alumoxane, and ionizing activators, and a support, wherein the activator and the catalyst are premixed in a solvent, and then combined with the support and then dried, to produce a free - flowing powder, and wherein the catalyst has a catalyst productivity of greater than  1000   ( g polymer )/( g catalyst*h* 150  psi )  at  85 ° C.   
     
     
       30. A continuous gas- phase process for polymerizing olefins, excluding cyclic olefin ( s ) , comprising: combining a )  one or more of ethylene, propylene, butene -   1 , pentene -   1 ,  4   - methyl -   1   - pentene, hexene -   1  and octene -   1  b )  a catalyst consisting essentially of a bis n - propyl cyclopentadienyl hafnium dichloride, an activator selected from the group consisting of alumoxane, methyl alumoxane, modified alumoxane, and ionizing activators, and a support, wherein the activator and catalyst are premixed in a solvent, and then combined with the support and then dried, to produce a free - flowing powder, and wherein the catalyst has a catalyst productivity of greater than  1000   ( g polymer )/( g catalyst*h* 150  psi )  at  85 ° C.   
     
     
       31. A continuous gas- phase process for polymerizing olefins, excluding cyclic olefin ( s ) , comprising: combining a )  one or more of ethylene, propylene, butene -   1 , pentene -   1 ,  4   - methyl -   1   - pentene, hexene -   1  and octene -   1  b )  a catalyst consisting of a bis n - propyl cyclopentadienyl hafnium dichloride, an activator selected from the group consisting of alumoxane, methyl alumoxane, modified alumoxane, and ionizing activators, and a support, wherein the activator and the catalyst are premixed in a solvent, and then combined with the support and then dried, to produce a free - flowing powder, and wherein the catalyst has a catalyst productivity of greater than  1000   ( g polymer )/( g catalyst*h* 150  psi )  at  85 ° C.