Polymerization process

Abstract

The invention provides for polymerization catalyst compositions, and for methods for introducing the catalyst compositions into a polymerization reactor. More particularly, the method combines a catalyst component containing slurry and a catalyst component containing solution to form the completed catalyst composition for introduction into the polymerization reactor. The invention is also directed to methods of preparing the catalyst component slurry, the catalyst component solution and the catalyst compositions, to methods of controlling the properties of polymer products utilizing the catalyst compositions, and to polymers produced therefrom.

1 . A catalyst composition comprising: 
 (a) a solid portion comprising a support, a Group 15 containing catalyst compound, an activator, and a metallocene catalyst compound; the support pretreated with the catalyst compounds and activator;    (b) and a diluent comprising mineral oil.    
     
     
         2 . The catalyst composition of  claim 1 , wherein from 1 to 40 μmol of total catalyst compounds are present per gram of support.  
     
     
         3 . The catalyst composition of  claim 1 , wherein the solid portion comprises from 5 to 40 wt % of the composition.  
     
     
         4 . The catalyst composition of  claim 1 , wherein the support is an inorganic oxide comprising Group 2, 3, 4, 5, 13 or 14 metal oxides.  
     
     
         5 . The catalyst composition of  claim 1 , wherein the support comprises silica, fumed silica, alumina, silica-alumina and mixtures thereof.  
     
     
         6 . The catalyst composition of  claim 1 , wherein the support is fumed silica.  
     
     
         7 . The catalyst composition of  claim 1 , wherein the solid portion has an average particle size ranging from 10 to 40 microns.  
     
     
         8 . The catalyst composition of  claim 1 , wherein the catalyst composition has a viscosity of about 130 cP to about 2000 cP at 20° C.  
     
     
         9 . The catalyst composition of  claim 1 , wherein the activator comprises methylalumoxane or modified methylalumoxane.  
     
     
         10 . The catalyst composition of  claim 9 , wherein the molar ratio of aluminum to catalyst compound metal ranges from 300:1 to 1:1.  
     
     
         11 . The catalyst composition of  claim 1 , wherein the Group 15 containing catalyst is represented by the formula:  
       
         
           
           
               
               
           
         
       
       wherein 
 M is a Group 4, 5 or 6 transition metal;  
 each X is independently an anionic leaving group;  
 n is the oxidation state of M;  
 m is the formal charge of the YZL ligand;  
 L is a Group 15 or 16 element;  
 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, the heteroatom being silicon, germanium, tin, lead, or phosphorus;  
 R 3  is absent or a hydrocarbon group, hydrogen, a halogen, a heteroatom containing group;  
 R 4  and R 5  are independently an alkyl group, an aryl group, substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic arylalkyl group, a substituted cyclic arylalkyl group or multiple ring system; and  
 R 6  and R 7  are independently absent, or hydrogen, an alkyl group, halogen, heteroatom or a hydrocarbyl group.  
 
     
     
         12 . The catalyst composition of  claim 11 , wherein M is a Group 4 metal.  
     
     
         13 . The catalyst composition of  claim 11 , wherein L, Y and Z are nitrogen.  
     
     
         14 . The catalyst composition of  claim 11 , wherein R 6  and R 7  are absent; and wherein R 4  and R 5  are independently a group represented by the following formula:  
       
         
           
           
               
               
           
         
       
       wherein R 8  to R 12  are each independently hydrogen, a C 1  to C 40  alkyl group, a halide or a heteroatom containing group containing up to 40 carbon atoms.  
     
     
         15 . The catalyst composition of  claim 1 , wherein the metallocene catalyst compound in the slurry, solution, or both is represented by the following formulae:  
         L A L B MQ n  and L A AL B MQ n    
       wherein M is a Group 4, 5 or 6 transition metal; 
 L A  and L B  are each bound to M and are independently selected from unsubstituted or substituted versions of cyclopentadienyl ligands, cyclopentadienyl-type ligands, heteroatom substituted, and heteroatom containing cyclopentadienyl-type ligands;  
 each Q is bound to M and is independently an amine, phosphine, alkoxy, carboxylate, diene, hydrocarbyl radical having from 1 to 20 carbon atoms, hydride or halogen or a combination thereof;  
 A is a divalent bridging group bound to each of L A  and L B  containing at least one Group 13 to 16 atom; and  
 n is 0, 1 or2.  
 
     
     
         16 . The catalyst composition of  claim 15 , wherein M is a Group 4 metal.  
     
     
         17 . The catalyst composition of  claim 15 , wherein L A  and L B  are independently selected from substituted and unsubstituted versions of cyclopentadienyl, cyclopentaphenanthreneyl, indenyl, benzindenyl, fluorenyl, octahydrofluorenyl, and tetrahydroindenyl ligands.  
     
     
         18 . The catalyst composition of  claim 17 , wherein the ligands comprise one or more substituent groups selected from methyl, ethyl, propyl, butyl pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl groups.  
     
     
         19 . The catalyst composition of  claim 1 , wherein the composition comprises a supported alumoxane, a Group 15 catalyst compound and a metallocene catalyst compound; wherein the metallocene catalyst compound is bis(n-propyl cyclopentadienyl)MX 2 , (pentamethylcyclopentadienyl)(n-propylcyclopentadienyl)MX 2,  bis(indenyl)MX 2 , or (tetramethylcyclopentadienyl)(n-propyl cyclopentadienyl)MX 2 , where M is zirconium, hafnium or titanium and X is chlorine, bromine, or fluorine.  
     
     
         20 . The catalyst composition of  claim 1 , further comprising a catalyst component solution comprising a metallocene catalyst component and a C 5  to C 30  alkane diluent.  
     
     
         21 . The catalyst composition of  claim 20 , wherein the metallocene is the same as the metallocene in the solid portion of the composition.  
     
     
         22 . The catalyst composition of  claim 1 , wherein the composition is capable of producing a bimodal (polyethylene-co-{C 2  to C 8  olefin}) resin having a density of 0.93 to 0.96 g/cm 3 , an I 2  of 0.03 to 0.10 g/10 min, an I 21  of 4 to 12 g/10 min, and I 21 /I 2  of 80 to 180, an overall M w  of 200,000 to 400,000, and overall M n  of 5,000 to 10,000, and an M w /M n  of 20-50.