Delayed activity supported olefin polymerization catalyst compositions and method for making and using the same

Abstract

A supported catalyst and methods for making and using the same, by employing organometallic Group 4-10 catalysts with specially selected dienes, which, when combined with a cocatalyst, result in a supported catalyst which has improved kinetic profiles in the gas polymerization process.

We claim:  
     
         1 . A method for preparing an olefin polymerization catalyst comprising: 
 (a) selecting a metal complex which corresponds to the formula:                          wherein Cp is an anionic, delocalized, π-bonded group that is bound to M, containing up to 50 nonhydrogen atoms;    M is a metal of Group 4 of the Periodic Table of the Elements in the +2 or +4 formal oxidation state;    X is a C 4-30  conjugated diene represented by the formula:                          wherein R 1 , R 2 , R 3 , and R 4  were each independently hydrogen, aromatic, substituted aromatic, fused aromatic, substituted fused aromatic, aliphatic, substituted aliphatic, heteroatom-containing aromatic, heteroatom-containing fused aromatic, or silyl radical;;    Y is —O—, —S—, —NR—, or —PR—; and    Z is SiR 2 , CR 2 , SiR 2 SiR 2 .CR 2 CR 2 , CR═CR, CR 2 SiR 2 , or GeR 2 , BR 2 , B(NR 2 ) 2 , BR 2 BR 2 , B(NR 2 ) 2 B(NR 2 ) 2 ,    wherein R is in each occurrence independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, said R having up to 20 non-hydrogen atoms, or adjacent R groups together form a divalent derivative (that is, a hydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fused ring system.    (b) selecting a cocatalyst from the group consisting of polymeric or oligomeric alumoxanes; neutral Lewis acids; nonpolymeric, compatible, noncoordinating, ion forming compounds; and combinations thereof;    (c) supporting the metal complex and the cocatalyst upon a support, wherein the catalyst composition, when injected into gas phase polymerization batch reactor, and contacted with ethylene, demonstrates a kinetic profile which obeys the following inequality:      K   r   =A   30   /A   90 ≦1.6    where Kr refers to the cumulative net activity in grams polymer/gram catalyst hr bar ethylene at 30 minutes after the onset of polymerization (A 30 ) divided by the net activity in grams polymer/gram catalyst hr bar at 90 minutes after the onset of polymerization (A 9O ).    
     
     
         2 . A method for preparing an olefin polymerization catalyst comprising: 
 (a) selecting a metal complex which corresponds to the formula:                          wherein D is an anionic, delocalized, π-bonded group that is bound to M, containing up to 50 nonhydrogen atoms;    M is a metal of Group 4 of the Periodic Table of the Elements in the +2 or +4 formal oxidation state;    X is a C 4-30  conjugated diene represented by the formula:                          wherein R 1 , R 2 , R 3  and R 4  were each independently hydrogen, aromatic, substituted aromatic, fused aromatic, substituted fused aromatic, aliphatic, substituted aliphatic, heteroatom-containing aromatic, heteroatom-containing fused aromatic, or silyl radical;;    Y is —O—, —S—, —NR—, or —PR—; and    Z is SiR 2 , CR 2 , SiR 2 SiR 2 , CR 2 CR 2 , CR═CR, CR 2 SiR 2 , or GeR 2 , BR 2 , B(NR 2 ) 2 , BR 2 BR 2 , B(NR 2 ) 2 B(NR 2 ) 2 ,    wherein R is in each occurrence independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, said R having up to 20 non-hydrogen atoms, or adjacent R groups together form a divalent derivative (that is, a hydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fused ring system.    (b) selecting a cocatalyst from the group consisting of polymeric or oligomeric alumoxanes; neutral Lewis acids; nonpolymeric, compatible, noncoordinating, ion forming compounds; and combinations thereof;    (c) supporting the metal complex and the cocatalyst upon a support,    wherein the catalyst composition, when injected into gas phase polymerization batch reactor, and contacted with ethylene, demonstrates a demonstrates a K, which is at least 10 percent less than the K r  for a comparative supported catalyst composition prepared using [tetramethylcyclopentadienyl(dimethylsilyl)(n-t-butylamido)]titanium(II)piperylene and a tetrakis(pentafluorophenyl)borate salt of a long chain alkyl mono- and disubstituted ammonium complex, wherein    Kr refers to the cumulative net activity in grams polymer/gram catalyst hr bar ethylene at 30 minutes after the onset of polymerization (A 30 ) divided by the net activity in grams polymer/gram catalyst hr bar at 90 minutes after the onset of polymerization (A 90 ).    
     
     
         3 . The method of claims  1  or  2 , wherein the metal complex corresponds to the formula:  
       
         
           
           
               
               
           
         
         wherein:  
         M is titanium, zirconium or hafnium in the +2 or +4 formal oxidation state;  
         R in each occurrence independently is selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, said R having up to 20 non-hydrogen atoms, or adjacent R groups together form a divalent derivative (that is, a hydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fused ring system,  
         each X is a C 4-30  conjugated diene represented by the formula:  
         
           
             
             
                 
                 
             
           
         
         wherein R 1 , R 2 , R 3 , and R 4  are each independently aromatic, substituted aromatic, fused aromatic, substituted fused aromatic, aliphatic, substituted aliphatic, heteroatom-containing aromatic, heteroatom-containing fused aromatic, or silyl radical;  
         Y is —O—, —S—, —NR*—, —PR*—; and  
         Z is SiR* 2 , CR* 2 , SiR* 2 SiR* 2 , CR* 2 CR* 2 , CR*═CR*, CR* 2 SiR* 2 , or GeR* 2 , wherein R* independently at each occurrence is hydrogen or a group selected from silyl, hydrocarbyl, hydrocarbyloxy and combinations thereof, said R* having up to 30 carbon or silicon atoms.  
       
     
     
         4 . The method of claims  1  or  2 : 
 wherein each X is a C 6-30  conjugated diene represented by the formula:  
                     
 wherein R 1 , R 2 , R 3 , and R 4  are each independently aromatic, substituted aromatic, fused aromatic, substituted fused aromatic, aliphatic, substituted aliphatic, heteroatom-containing aromatic, heteroatom-containing fused aromatic, or silyl radical.  
 
     
     
         5 . The method of claims  1  or  2 , wherein the cocatalyst is represented by the following general formula:  
       (L*−H) d   + (A′) d−   
       wherein: 
 L* is a neutral Lewis base;  
 (L*−H) +  is a Bronsted acid;  
 A′ d−  is a noncoordinating, compatible anion having a charge of d−, and  
 d is an integer from 1 to 3.  
 More preferably A′ d−  corresponds to the formula: [M*Q 4 ] − ;  
 wherein:  
 M* is boron or aluminum in the +3 formal oxidation state; and  
 Q independently each occurrence is selected from hydride, dialkylamido, halide, hydrocarbyl, halohydrocarbyl, halocarbyl, hydrocarbyloxide, hydrocarbyloxy substituted-hydrocarbyl, organometal substituted-hydrocarbyl, organometalloid substituted-hydrocarbyl, halohydrocarbyloxy, halohydrocarbyloxy substituted hydrocarbyl, halocarbyl-substituted hydrocarbyl, and halo-substituted silylhydrocarbyl radicals (including perhalogenated hydrocarbyl-perhalogenated hydrocarbyloxy- and perhalogenated silylhydrocarbyl radicals), said Q having up to 20 carbons with the proviso that in not more than one occurrence is Q halide.  
 
     
     
         6 . The method of claims  1  or  2 , wherein the cocatalyst is represented by the formula:  
       (L*−H) + (BQ 4 );  
       wherein: 
 L* is a neutral Lewis base;  
 B is boron in a formal oxidation state of 3; and  
 Q is a hydrocarbyl-, hydrocarbyloxy-, fluorinated hydrocarbyl-, fluorinated hydrocarbyloxy-, or fluorinated silylhydrocarbyl-group of up to 20 nonhydrogen atoms, with the proviso that in not more than one occasion is Q hydrocarbyl.  
 
     
     
         7 . The method of claims  1  or  2 , wherein the cocatalyst is represented by the formula:  
       [L*−H] + [(C 6 F 5 ) 3 BC 6 H 4 —O—M 0 R C   x−1 X a   y ] − ,  wherein M 0  is a metal or metalloid selected from Groups 1-14 of the Periodic Table of the Elements,    R C  independently each occurrence is hydrogen or a group having from 1 to 80 nonhydrogen atoms which is hydrocarbyl, hydrocarbylsilyl, or hydrocarbylsilylhydrocarbyl;    X a  is a noninterfering group having from 1 to 100 nonhydrogen atoms which is halo-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino, di(hydrocarbyl)amino, hydrocarbyloxy or halide;    x is a nonzero integer which may range from 1 to an integer equal to the valence of M 0 ;    y is zero or a nonzero integer which may range from 1 to an integer equal to 1 less than the valence of M 0 ; and    x+y equals the valence of M 0 .    
     
     
         8 . The method of claims  1  or  2 , wherein R1 and R2 are each a benzyl radical or substituted benzyl radical.  
     
     
         9 . The method of claims  1  or  2 , wherein R1 and R2 are each a phenyl radical or substituted phenyl radical.  
     
     
         10 . A supported catalyst composition comprising: 
 (a) a metal complex corresponding to the formula:                          wherein D is an anionic. delocalized, π-bonded group that is bound to M, containing up to 50 nonhydrogen atoms;    M is a metal of Group 4 of the Periodic Table of the Elements in the +2 or +4 formal oxidation state;    X is a C 4-30  conjugated diene represented by the formula:                          wherein R1 and R2 are each independently aromatic, substituted aromatic, C 1 -C 20  aliphatic, substituted aliphatic, heteroatom-containing aromatic, or silyl radical;    Y is —O—, —S—, —NR*—, —PR*—; and    Z is SiR* 2 , CR* 2 , SiR* 2 SiR* 2 , CR* 2 CR* 2 , CR*=CR*, CR* 2 SiR* 2 , or GeR* 2 , wherein R* independently at each occurrence is hydrogen or a group selected from silyl, hydrocarbyl, hydrocarbyloxy and combinations thereof, said R* having up to 30 carbon or silicon atoms;    (b) a cocatalyst selected from the group consisting of polymeric or oligomeric alumoxanes; neutral Lewis acids; nonpolymeric, compatible, noncoordinating, ion forming compounds; and combinations thereof;    (c) a support,    wherein the catalyst composition, when injected into gas phase polymerization batch reactor, and contacted with ethylene, demonstrates a kinetic profile which obeys the following inequality:      K   r   =A   30   /A   90 ≦1.6    where Kr refers to the cumulative net activity in grams polymer/gram catalyst hr bar ethylene at 30 minutes after the onset of polymerization (A 30 ) divided by the net activity in grams polymer/gram catalyst hr −  bar at 90 minutes after the onset of polymerization (A 90 ).    
     
     
         11 . A supported catalyst composition comprising: 
 (a) a metal complex corresponding to the formula:                          wherein D is an anionic, delocalized, π-bonded group that is bound to M, containing up to 50 nonhydrogen atoms;    M is a metal of Group 4 of the Periodic Table of the Elements in the +2 or +4 formal oxidation state;    X is a C 4-30  conjugated diene represented by the formula:                          wherein R1 and R2 are each independently aromatic, substituted aromatic, C 1 -C 20  aliphatic, substituted aliphatic, heteroatom-containing aromatic, or silyl radical;    Y is —O—, —S—, —NR*—, —PR*—; and    Z is SiR* 2 , CR* 2 , SiR* 2 SiR* 2 , CR* 2 CR* 2 , CR*=CR*, CR* 2 SiR* 2 , or GeR* 2 , wherein R* independently at each occurrence is hydrogen or a group selected from silyl, hydrocarbyl, hydrocarbyloxy and combinations thereof, said R* having up to 30 carbon or silicon atoms;    (b) a cocatalyst selected from the group consisting of polymeric or oligomeric alumoxanes; neutral Lewis acids; nonpolymeric, compatible, noncoordinating, ion forming compounds; and combinations thereof;    (c) a support,    wherein the catalyst composition, when injected into gas phase polymerization batch reactor, and contacted with ethylene, demonstrates a demonstrates a K, which is at least 10 percent less than the K r  for a comparative supported catalyst composition prepared using [tetramethylcyclopentadienyl(dimethylsilyl)(n-t-butylamido)]titanium(II)piperylene and a tetrakis(pentafluorophenyl)borate salt of a long chain alkyl mono- and disubstituted ammonium complex, wherein    Kr refers to the cumulative net activity in grams polymer/gram catalyst hr bar ethylene at 30 minutes after the onset of polymerization (A 30 ) divided by the net activity in grams polymer/gram catalyst hr bar at 90 minutes after the onset of polymerization (A 90 ).    
     
     
         12 . The supported catalyst composition of claims  10  or  11 , wherein R1 and R2 are each a benzyl radical or substituted benzyl radical.  
     
     
         13 . The supported catalyst composition of claims  10  or  11 , wherein R1 and R2 are each a phenyl radical or substituted phenyl radical.  
     
     
         14 . A catalyst composition comprising: 
 A) an inert support,    B) a Group 4-10 metal complex corresponding to the formula:                          where M is a metal from one of Groups 4 to 10 of the Periodic Table of the Elements, which is in the +2 or +4 formal oxidation state,    Cp is a π-bonded anionic ligand group    Z is a divalent moiety bound to Cp and bound to M by either covalent or coordinate/covalent bonds, comprising boron or a member of Group 14 of the Periodic Table of the Elements, and also comprising nitrogen, phosphorus, sulfur or oxygen;    X is a neutral conjugated diene ligand group having up to 60 atoms, or a dianionic derivative thereof; and    C) an ionic cocatalyst capable of converting the metal complex into an active polymerization catalyst,    wherein said catalyst composition is characterized as having an improved kinetic profile in a gas phase polymerization process.    
     
     
         15 . The catalyst composition of  claim 13  having a kinetic profile in a batch reactor, gas phase polymerization of one or more a-olefins that obeys the following relationship:  
         K   r   =A   30   /A   90 ≦1.6  where K r  is the ratio of the cumulative net catalyst activity 30 minutes after onset of polymerization (A 30 ) divided by the cumulative net catalyst activity 90 minutes after onset of polymerization (A 90 ). A 30  and A 90  are determined by calculating the grams polymer/gram supported catalyst composition×time (hr)×total monomer pressure (100 kPa).    
     
     
         16 . The composition of  claim 14  wherein the supported catalyst composition, when injected into a gas phase polymerization reactor, and contacted with one or more α-olefin monomers, demonstrates a K r  which is at least 10 percent less than K* r , where K*, is the ratio of cumulative net catalyst activity for a comparative supported catalyst composition prepared using the metal complex (t-butylamido)dimethyl-(tetramethylcyclopentadienyl)silanetitanium(II) 1,3-pentadiene and a cocatalyst comprising armenium (diethylaluminumoxyphenyl)tris-(pentafluorophenyl)borate.