Coordination catalyst systems employing agglomerated metal oxide/clay support-activator and method of their preparation

Abstract

The present invention is directed to a coordinating catalyst system comprising at least one bidentate or tridentate pre-catalyst transition metal compound, (e.g., 2,6-bis (2,4,6-trimethylarylamino) pyridyl iron dichloride), at least one support-activator (e.g., spray dried silica/clay agglomerate), and optionally at least one organometallic compound (e.g., triisobutyl aluminum), in controlled amounts, and methods for preparing the same. The resulting catalyst system exhibits enhanced activity for polymerizing olefins and yields polymer having very good morphology.

What is claimed is:  
     
         1 . A coordinating catalyst system capable of polymerizing olefins comprising: 
 (I) as a pre-catalyst, at least one non-metallocene, non-constrained geometry, bidentate transition metal compound or tridentate transition metal compound capable of (A) being activated upon contact with the support-activator of (II)(B) or (B) being converted, upon contact with an organometallic compound, to an intermediate capable of being activated upon contact with the support-activator of (II)(B), wherein the transition metal is at least one member selected from Groups 3 to 10 of the Periodic table; in intimate contact with    (II) catalyst support-activator agglomerate comprising a composite of (A) at least one inorganic oxide component selected from SiO 2 , Al 2 O 3 , MgO, AlPO 4 , TiO 2 , ZrO2, Cr 2 O 3  and (B) at least one ion containing layered material having interspaces between the layers and sufficient Lewis acidity, when present within the support-activator, to activate the pre-catalyst when the pre-catalyst is in contact with the support-activator, said layered material having a cationic component and an anionic component, wherein said an anionic component is present within the interspace of the layered material, said layered material being intimately dispersed with said inorganic oxide component within the agglomerate in an amount sufficient to improve the activity of the coordinating catalyst system for polymerizing ethylene monomer, expressed as Kg of polyethylene per gram of catalyst system per hour, relative to the activity of a corresponding catalyst system employing the same pre-catalyst but in the absence of either Component A or B of the support-activator; wherein the amount of the pre-catalyst and support-activator which is in intimate contact is sufficient to provide a ratio of micromoles of pre-catalyst to grams of support-activator of from about 5:1 to about 500:1.    
     
     
         2 . The catalyst system of  claim 1  which additionally comprises as a third component, at least one organometallic compound represented by the structural formula:  
       M(R 12 ) s    
       wherein M represents at least one element of Group 1, 2, or 13 or the Periodic Table, tin or zinc, and each R 2  independently represents at least one of hydrogen, halogen, or hydrocarbon-based group, and “s” is a number corresponding to the oxidation number of M; said organometallic compound being in intimate contact with said pre-catalyst in an amount sufficient to provide a molar ratio of organometallic compound to pre-catalyst from about 0.001:1 to about 10,000:1.  
     
     
         3 . The catalyst system of  claim 1  wherein the pre-catalyst is a bidentate transition metal compound represented by the formula:  
       
         
           
           
               
               
           
         
       
       wherein: 
 (I) each A independently represents oxygen, sulfur, phosphorus or nitrogen;  
 (II) Z represents a transition metal selected from at least one of the group of Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt in the +2 oxidation state, and Ti, V, Cr, Mn, Zr, and Hf in the +2, +3 or +4 oxidation state:  
 (III) each L and L′ independently represents a ligand group selected from at least one of hydrogen, halogen, hydrocarbon based radical, or two L groups, together represent a hydrocarbon based radical, which, together with Z, constitute a heterocyclic ring structure;  
 (IV) “a” is an integer of 0 or 1 and represents the number of L′ groups bound to Z, the lines joining each A to each other A represent a hydrocarbon based radical joined to A by a double or single bond, the lines joining each A to Z represent a covalent or dative bond.  
 
     
     
         4 . The catalyst system of  claim 1  wherein the transition metal compound is a tridentate transition metal compound represented by the formula:  
       
         
           
           
               
               
           
         
       
       wherein: 
 (I) each A independently represents oxygen, sulfur, phosphorous or nitrogen;  
 (II) Z represents a transition metal selected from at least one of the group of Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt in the +2 oxidation state and Ti, V, Cr, Mn, Zr, and Hf in the +2, +3 or +4 oxidation state;  
 (III) each L and L′ independently represents a ligand group selected from at least one of hydrogen, halogen and hydrocarbon based radical, or two L groups together represent a hydrocarbon based radical, which together with Z, constitute a heterocyclic ring structure; and  
 (IV) “a” is an integer of 0, 1, or 2 and represents the number of L′ groups bound to Z, the lines joining each A to each other A represent a hydrocarbon based radical joined to A by a double or single bond, and the lines joining each A to Z represent a covalent or dative bond.  
 
     
     
         5 . The catalyst system of any one of claims  3  and  4  wherein each A represents a nitrogen atom, each L and L′ is independently selected from halogen, hydrocarbyl or mixtures thereof, or two L groups together represent hydrocarbylene which together with Z constitute a 3 to 7 member heterocyclic ring structure.  
     
     
         6 . The catalyst system of any one of claims  3  and  4  wherein at least one L of the pre-catalyst is selected from hydrocarbyl.  
     
     
         7 . The catalyst system of  claim 6  wherein Z is selected from Ni, Pd, Fe or Co.  
     
     
         8 . The catalyst system of  claim 3  wherein Z is selected from Ni or Pd and each L is independently selected from chlorine, bromine, iodine, or C 1 -C 8  alkyl.  
     
     
         9 . The catalyst system of  claim 4  wherein Z is selected from iron or cobalt and each L is independently selected from chlorine, bromine, iodine, or C 1 -C 8  alkyl.  
     
     
         10 . The catalyst system of any one of claims  3  and  4  wherein L is selected from halogen or hydrogen, and the catalyst system further comprises at least one organometallic compound represented by the formula:  
       M(R 12 ) s    
       wherein M is aluminum R 12  is hydrocarbyl, and “s” is 3, intimately associated with the pre-catalyst in an amount sufficient to provide a molar ratio of organometallic compound to transition metal in the pre-catalyst of from about 0.001:1 to about 250:1.  
     
     
         11 . The catalyst system of  claim 1  wherein the layered material of the support-activator is at least one of clay or clay minerals having a negative charge of below 0.  
     
     
         12 . The catalyst system of  claim 11  wherein the layered material is a smectite clay, the weight ratio of inorganic oxide to clay in the support activator agglomerate is from about 0.25:1 to about 99:1, and the ratio of micromoles of pre-catalyst to grams of support-activator is from about 10:1 to about 250:1.  
     
     
         13 . The catalyst system of  claim 12  wherein the smectite clay is at least one of montmorillonite and hectorite, the weight ratio of inorganic oxide to clay in the support-activator agglomerate is from about 0.5:1 to about 20:1, and the ratio of micromoles of pre-catalyst to grams of support-activator is from about 30:1 to about 100:1.  
     
     
         14 . The catalyst system of  claim 1  wherein the inorganic oxide component is SiO 2 , the weight ratio of SiO 2  to layered material in the support-activator agglomerate is from about 1:1 to about 10:1, and the ratio of micromoles of pre-catalyst to grams of support-activator is from about 80:1 to about 100:1.  
     
     
         15 . The catalyst system of anyone of claims  1  and  2  wherein the support-activator comprises spray dried agglomerate particles comprising constituent particles of at least one of said inorganic oxides and at least one of said layered materials wherein: 
 (I) at least 80% of the volume of the agglomerated particles smaller than D 90  of the entire agglomerate particle size distribution possesses a microspheroidal morphology;  
 (II) the support-activator agglomerate particles possess: 
 (A) an average particle size of from about 4 to about 250 microns, and  
 (B) a surface area of from 20 to about 800 m 2 /gm; and  
 
 (III) the constituent inorganic oxide particles from which the agglomerate particles are derived have an average particle size, prior to spray drying of from about 2 to about 10 microns, and the constituent layered material particles have an average particle size, prior to spray drying of from about 0.01 to about 50 microns.  
 
     
     
         16 . The catalyst system of  claim 15  wherein the constituent inorganic oxide particles from which the agglomerate particles are derived, prior to spray drying, have: 
 (I) an average particle size of from about 4 to about 9 microns,  
 (II) a particle size Distribution Span of from about 0.5 to about 3.0 microns, and  
 (III) a colloidal particle size content of from about 2 to about 60 wt. %, based on the constituent inorganic oxide particle weight.  
 
     
     
         17 . A coordinating catalyst system formed by the process comprising: 
 (I) agglomerating to form a support-activator: 
 (A) at least one inorganic oxide component selected from SiO 2 , Al 2 O 3 , MgO, AlPO 4 , TiO 2 , ZrO 2 , Cr 2 O 3  with  
 (B) at least one ion containing layered material having interspaces between the layers and sufficient Lewis acidity, when present within the support-activator, to activate the transition metal of the pre-catalyst of II when the pre-catalyst is in contact with the support-activator, said layered material, having a cationic component and an anionic component, wherein said anionic component is present within the interspace of the layered material, said layered material being intimately dispersed with said inorganic oxide component within said agglomerate in an amount sufficient to improve the activity of the coordinating catalyst system for polymerizing ethylene monomer, expressed as Kg of polyethylene per gram of catalyst system per hour, relative to the activity of a corresponding catalyst system employing the same pre-catalyst but in the absence of either Component A or B of the support-activator;  
   (II) providing as a pre-catalyst, at least one non-metallocene, non-constrained geometry, transition metal compound selected from bidentate transition metal compound, and tridentate transition metal compound capable of (A) being activated upon contact with the support-activator of (I), or (B) being converted, upon contact with an organometallic compound, to an intermediate capable of being activated upon contact with the support-activator, wherein the transition metal is at least one element selected from Groups 3 to 10 of the Periodic Table;    (III) contacting the support-activator and pre-catalyst in the presence of at least one inert liquid hydrocarbon in a manner sufficient to provide a ratio of micromoles of pre-catalyst to grams of support-activator of from about 5:1 to about 500:1.    
     
     
         18 . The catalyst system of  claim 17  prepared by the additional step of including at least one organometallic compound in the liquid hydrocarbon of step III, said organometallic compound being represented by the structure formula:  
       M(R 12 ) s    
       wherein M represents at least one element of Groups 1, 2, or 13 of the Periodic Table, tin or zinc, and each R 12  independently represents at least one of hydrogen, halogen, or hydrocarbon-based group, and “s” is a number corresponding to the oxidation number of M, said organometallic compound being in intimate contact with said pre-catalyst, wherein the amount of organometallic compound present is sufficient to provide a molar ratio of organometallic compound to pre-catalyst of from about 0.001:1 to about 250:1.  
     
     
         19 . The catalyst system of  claim 17  wherein the transition metal compound is a bidentate transition metal compound represented by the formula:  
       
         
           
           
               
               
           
         
       
       wherein: 
 (I) each A independently represents oxygen, sulfur, phosphorus or nitrogen;  
 (II) Z represents a transition metal selected from at least one of the group of Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt in the +2 oxidation state, and Ti, V, Cr, Mn, Zr, and Hf in the +2, +3 or +4 oxidation state;  
 (III) each L and L′ independently represents a ligand group selected from at least one of hydrogen, halogen, and hydrocarbon based radical, or two L groups together represent a hydrocarbon based radical which, together with Z, constitute a heterocyclic ring structure; and  
 (IV) “a” is an integer of 0 or 1 and represents the number of L′ groups bound to Z, the lines joining each A to each other A represent a hydrocarbon based radical joined to A by a double or single bond, and the lines joining each A to Z represent a covalent or dative bond.  
 
     
     
         20 . The catalyst system of  claim 17  wherein the transition metal compound is a tridentate transition metal compound represented by the formula:  
       
         
           
           
               
               
           
         
       
       wherein: 
 (I) each A independently represents oxygen, sulfur, phosphorous or nitrogen;  
 (II) Z represents a transition metal selected from at least one member of the group of Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt in the +2 oxidation state and Ti, V, Cr, Mn, Zr, and Hf in the +2, +3 or +4 oxidation state;  
 (III) each L and L′ independently represents a ligand group selected from at least one of hydrogen, halogen, and hydrocarbon based radical, or two L groups together represent a hydrocarbon based radical which, together with Z, constitute a heterocyclic ring structure; and  
 (IV) “a” is an integer of 0, 1 or 2 and represents the number of L′ groups bound to Z, the lines joining each A to each other A represent a hydrocarbon based radical joined to A by a double or single bond, and the lines joining each A to Z represent a covalent or dative bond.  
 
     
     
         21 . The catalyst system of any one of claims  19  and  20  wherein each A represents nitrogen, each L and L′ is independently halogen, hydrocarbyl, or mixtures thereof, or two L groups together represent a hydrocarbylene group which, together with Z, constitute a 3 to 7 member heterocyclic ring structure.  
     
     
         22 . The catalyst system of  claim 18  wherein M is aluminum, “s” is 3, and R 12  is C 1  to C 24  alkyl, and each L of the pre-catalyst is selected from halogen.  
     
     
         23 . The catalyst composition of any one of claims  19  and  20  wherein at least one L of the pre-catalyst is hydrocarbyl.  
     
     
         24 . The catalyst system of any one of claims  19  and  20  wherein Z is selected from at least one of Ni, Pd, Fe, or Co.  
     
     
         25 . The catalyst system of  claim 19  wherein Z is selected from Ni or Pd and each L is independently selected from chlorine, bromine, iodine, and C 1 -C 8  alkyl.  
     
     
         26 . The catalyst system of  claim 20  wherein Z is selected from iron and cobalt and each L is independently selected from chlorine, bromine, iodine, and C 1 -C 8  alkyl.  
     
     
         27 . The catalyst system of  claim 19  prepared by the additional step of including in the inert hydrocarbon liquid of step III, at least one organometallic compound represented by the structural formula:  
       M(R 12 ) s    
       wherein M represents at least one element of Group 1, 2, or 13 or the Periodic Table, tin or zinc, and each R 12  independently represents at least one of hydrogen, halogen, or hydrocarbyl group, and “s” is the oxidation number of M; said organometallic compound being in intimate contact with said pre-catalyst in an amount sufficient to provide a molar ratio of organometallic compound to pre-catalyst of from about 0.01:1 to about 125:1.  
     
     
         28 . The catalyst system of  claim 20  prepared by the additional steps of including in the inert hydrocarbon liquid of step III, at least one organometallic compound represented by the structural formula:  
       M(R 12 ) s    
       wherein M represents at least one element of Group 1, 2, or 13 or the Periodic Table, tin or zinc, and each R 12  independently represents at least one of hydrogen, halogen, or hydrocarbyl group, and “s” is the oxidation number of M; said organometallic compound being in intimate contact with said pre-catalyst in an amount sufficient to provide a molar ratio of organometallic compound to pre-catalyst of from about 0.1:1 to about 10:1.  
     
     
         29 . The catalyst system of  claim 27  wherein M is aluminum, R 12  is alkyl or alkoxy, “s” is 3, Z is selected from at least one of Ni and Pd, and L is halogen.  
     
     
         30 . The catalyst system of  claim 28  wherein M is aluminum, R 12  is alkyl or alkoxy, “s” is 3, Z is selected from at least one of Fe or Co, and L is halogen.  
     
     
         31 . The catalyst system of  claim 17  wherein the support-activator is at least one of clay or clay mineral having a negative charge below 0.  
     
     
         32 . The catalyst system of  claim 31  wherein the layered material is a smectite clay, the weight ratio of inorganic oxide to clay in the support activator agglomerate is from about 0.25:1 to about 99:1, and the ratio of micromoles of pre-catalyst to grams of support-activator is from about 10:1 to about 250:1.  
     
     
         33 . The catalyst system of  claim 32  wherein the smectite clay is at least one of montmorillonite and hectorite, the weight ratio of inorganic oxide to clay in the support-activator agglomerate is from about 0.5:1 to about 20:1, and the ratio of micromoles of pre-catalyst to grams of support-activator is from about 30:1 to about 100:1.  
     
     
         34 . The catalyst system of  claim 17  wherein the inorganic oxide component is SiO 2 , the weight ration of SiO 2  to layered material in the support-activator agglomerate is from about 1:1 to about 10:1, and the ratio of micromoles of pre-catalyst to grams of support-activator is from about 80:1 to about 100:1.  
     
     
         35 . The catalyst system of any one of claims  17  and  18  wherein the support-activator comprises spray dried agglomerate particles comprising constituent particles of at least one of said inorganic oxides and at least one of said layered materials wherein: 
 (I) at least 80% of the volume of the agglomerated particles smaller than D 90  of the entire agglomerate particle size distribution possesses a microspheroidal morphology;  
 (II) the support-activator agglomerate particles possess: 
 (A) an average particle size of from about 4 to about 250 microns, and  
 (B) a surface area of from 20 to about 800 m 2 /gm;  
 
 (III) the constituent inorganic oxide particles from which the agglomerate particles are derived have an average particle size, prior to spray drying, of from about 2 to about 10 microns, and the constituent layered material particles have an average particle size, prior to spray drying, of from about 0.01 to about 50 microns.  
 
     
     
         36 . The catalyst system of  claim 35  wherein the constituent inorganic oxide particles from which the agglomerate particles are derived, prior to spray drying, have: 
 (I) an average particle size of from about 4 to about 9 microns,  
 (II) a particle size Distribution Span of from about 0.5 to about 3.0 microns, and  
 (III) and a colloidal particle size content of from about 2 to about 60 wt. %, based on the constituent inorganic oxide particle weight.  
 
     
     
         37 . A process for preparing a catalyst system for polymerizing olefins. comprising: 
 (I) agglomerating to form a support-activator: 
 (A) at least one inorganic oxide component selected from SiO 2 , Al 2 O 3 , MgO, AlPO 4 , TiO 2 , ZrO 2 , Cr 2 O 3  with  
 (B) at least one ion containing layered material having interspaces between the layers and sufficient Lewis acidity, when present within the support-activator, to activate the pre-catalyst compound of (II) when the pre-catalyst is in contact with the support-activator, said layered material having a cationic component and an anionic component, wherein said anionic component is present within the interspace of the layered material, said layered material being intimately dispersed with said inorganic oxide component within the agglomerate in amounts sufficient to improve the activity of the coordinating catalyst system for polymerizing ethylene monomer, expressed as Kg of polyethylene per gram of catalyst system per hour, relative to the activity of a corresponding catalyst system employing the same pre-catalyst but in the absence of either Component A or B of the support-activator;  
   (II) providing as a pre-catalyst, at least one non-metallocene, non-constrained geometry transition metal compound selected from bidentate transition metal compound, and tridentate transition metal compound, capable of (A) being activated upon contact with the support-activator, or (B) being converted, upon contact with an organometallic compound, to an intermediate capable of being activated upon contact with the support-activator, wherein the transition metal is at least one member selected from Groups 3 to 10 of the Periodic Table;    (III) contacting the support-activator and pre-catalyst in the presence of at least one inert liquid hydrocarbon in a manner sufficient to provide in the liquid hydrocarbon, a ratio of micromoles of pre-catalyst to grams of support-activator of from about 5:1 or to about 500:1, and to cause at least one of absorption and adsorption of the pre-catalyst by the support-activator.    
     
     
         38 . The process of  claim 37  further comprising including at least one organometallic compound in the inert liquid hydrocarbon of step III represented by the structure formula:  
       M(R 12 ) s    
       wherein M represents at least one element of Groups 1, 2, or 13 of the Periodic Table, tin or zinc, and each R 12  independently represents at least one of hydrogen, halogen, or hydrocarbon-based group, and “s” is the oxidation number of M, said organometallic compound being in intimate contact with said pre-catalyst, wherein the amount of organometallic compound present in the liquid hydrocarbon is sufficient to provide a molar ratio of organometallic compound to pre-catalyst of from about 0.001:1 to about 250:1.  
     
     
         39 . The process of  claim 37  wherein the transition metal compound is a bidentate transition metal compound represented by the formula:  
       
         
           
           
               
               
           
         
       
       wherein: 
 (I) each A independently represents oxygen, sulfur, phosphorus nitrogen;  
 (II) Z represents a transition metal selected from at least one of the group of Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt in the +2 oxidation state, and Ti, V, Cr, Mn, Zr, and Hf in the +2, +3 or +4 oxidation state;  
 (III) each L and L′ independently represents a ligand group selected from at least one of hydrogen, halogen, and hydrocarbon based radical, or two L groups together represent a hydrocarbon based radical, which together with Z, constitute a heterocyclic ring structure; and  
 (IV) “a” is an integer of 0 or 1 and represents the number of L′ groups bound to Z, the lines joining each A to each other A represent a hydrocarbon based radical joined to A by a double or single bond, and the lines joining each A to Z represent a covalent or dative bond.  
 
     
     
         40 . The process of  claim 37  wherein the transition metal compound is a tridentate transition metal compound represented by the formula:  
       
         
           
           
               
               
           
         
       
       wherein: 
 (I) each A independently represents oxygen, sulfur, phosphorous or nitrogen;  
 (II) Z represents a transition metal selected from at least one of the group of Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt in the +2 oxidation state and Ti, V, Cr, Mn, Zr, and Hf in the +2, +3 or +4 oxidation state;  
 (III) each L and L′ independently represents a ligand group selected from at least one of hydrogen, halogen, and hydrocarbon based radical, or two L groups together represent a hydrocarbon based radical which, together with Z, constitute, a heterocyclic ring structure; and  
 (IV) “a” is an integer of 0, 1 or 2 and represents the number of L′ groups bound to Z, the lines joining each A to each other A represent a hydrocarbon based radical joined to A by a double or single bond, and the lines joining each A to Z represent a covalent or dative bond.  
 
     
     
         41 . The process of any one of claims  39  and  40  wherein each A represents nitrogen, each L and L′ is independently selected from halogen, hydrocarbyl or mixtures thereof, or two L groups together represent a hydrocarbylene group which, together with Z, constitute a 3 to 7 member heterocyclic ring structure.  
     
     
         42 . The process of  claim 38  wherein M is aluminum, “s” is 3, and R 12  is C 1  to C 24  alkyl, and each L of the pre-catalyst is halogen.  
     
     
         43 . The process of any one of claims  39  and  40  wherein at least one L of the pre-catalyst is hydrocarbyl.  
     
     
         44 . The process of any one of claims  39  and  40  wherein Z is selected from at least one of Ni, Pd, Fe, or Co.  
     
     
         45 . The process of  claim 39  wherein Z is selected from Ni or Pd and each L is independently selected from chlorine, bromine, iodine, and C 1 -C 8  alkyl.  
     
     
         46 . The process of  claim 40  wherein Z is selected from iron or cobalt and each L is independently selected from chlorine , bromine, iodine, and C 1 -C 8  alkyl.  
     
     
         47 . The process of  claim 39  prepared by the additional step of including in the inert liquid hydrocarbon of step III, at least one organometallic compound represented by the structure formula:  
       M(R 12 ) s    
       wherein M represents at least one element of Group 1, 2, or 13 or the Periodic Table, tin or zinc, and each R 12  independently re presents at least one of hydrogen, halogen, or hydrocarbyl group, and “s” is the oxidation number of M; said organometallic compound being in intimate contact with said pre-catalyst in an amount sufficient to provide a molar ratio of pre-catalyst to organometallic compound from about 0.01:1 to about 125:1.  
     
     
         48 . The process of  claim 40  prepared by the additional step of including at least one organometallic compound in the inert liquid hydrocarbon of step III represented by the structure formula:  
       M(R 12 ) s    
       wherein M represents at least one element of Group 1, 2, or 13 or the Periodic Table, tin or zinc, and each R 12  independently represents at least one of hydrogen, halogen or hydrocarbyl group, and “s” is the oxidation number of M; said organometallic compound being in intimate contact with said pre-catalyst in an amount sufficient to provide a molar ratio of pre-catalyst to organometallic compound in the hydrocarbon liquid from about 0.1:1 to about 10:1.  
     
     
         49 . The process of  claim 47  wherein M is aluminum, R 12  is alkyl or alkoxy, “s” is 3, Z is selected from at least one of Ni, Pd, and L is halogen.  
     
     
         50 . The process of  claim 48  wherein M is aluminum, R 12  is alkyl or alkoxy, “s” is 3, Z is selected from at least one of Fe or Co, and L is halogen.  
     
     
         51 . The process of  claim 37  wherein the support-activator is at least one of clay or clay mineral having a negative charge below 0.  
     
     
         52 . The process of  claim 51  wherein the layered material is a smectite clay, the weight ratio of inorganic oxide to clay in the support activator agglomerate is from about 0.25:1 to about 99:1, and the ratio of micromoles of pre-catalyst to grams of support-activator is from about 10:1 to about 250:1.  
     
     
         53 . The process of  claim 52  wherein the smectite clay is at least one of montmorillonite and hectorite, the weight ratio of inorganic oxide to clay in the support-activator agglomerate is from about 0.5:1 to about 20:1, and the ratio of micromoles of transition metal in the pre-catalyst to grams of support-activator is from about 30:1 to about 100:1.  
     
     
         54 . The process of  claim 37  wherein the inorganic oxide is SiO 2 , the weight ratio of SiO 2  to layered material in the support-activator agglomerate is from about 1:1 to about 10:1, and the ratio of micromoles of pre-catalyst to grams of support-activator is from about 30:1 to about 100:1.  
     
     
         55 . The process of any one of claims  37  and  38  wherein the support-activator comprises spray dried agglomerate particles comprising constituent particles of at least one of said inorganic oxides and at least one of said layered materials wherein: 
 (I) at least 80% of the volume of the agglomerated particles smaller than D 90  of the entire agglomerate particle size distribution possesses a microspheroidal morphology;  
 (II) the support-activator agglomerate particles possess 
 (A) an average particle size of from about 5 to about 250 microns, and  
 (B) a surface area of from 20 to about 800 m 2 /gm;  
 
 (III) the constituent inorganic oxide particles from which the agglomerate particles are derived have an average particle size, prior to spray drying, of from about 2 to about 10 microns and the constituent layered material particles have an average particle size, prior to spray drying, of from about 0.01 to about 50 microns.  
 
     
     
         56 . The process of  claim 55  wherein the constituent inorganic oxide particles from which the agglomerate particles are derived, prior to spray drying, have: 
 (I) an average particle size of from about 4 to about 9 microns;  
 (II) a particle size Distribution Span of from about 0.5 to about 3.0 microns; and  
 (III) a colloidal particle size content of from about 2 to about 60 wt. %, based on the constituent inorganic oxide weight.  
 
     
     
         57 . The process of  claim 37  wherein the support-activator and pre-catalyst are agitated in the liquid hydrocarbon at a temperature of from about 0 to about 80° C. for a period of from about 0.5 to about 1440 minutes.  
     
     
         58 . The process of  claim 37  wherein the liquid hydrocarbon is separated from the mixture of support-activator and pre-catalyst.  
     
     
         59 . The process of  claim 38  wherein the liquid hydrocarbon is separated from the mixture of support-activator, pre-catalyst and organometallic compound.  
     
     
         60 . The process of  claim 38  wherein the organometallic compound is contacted with pre-catalyst prior to contract with the support-activator.  
     
     
         61 . The process of  claim 37  further comprising including in the inert liquid hydrocarbon of step III, at least one organometallic compound represented by the structural formula:  
       M(R 12 ) s    
       wherein M represents at least one element of Groups 1, 2, or 13 or the Periodic Table, tin or zinc, and each R 12  independently represents at least one of hydrogen, halogen, or hydrocarbyl group, and “s” is the oxidation number of M, said organometallic compound being in intimate contact with said pre-catalyst, wherein the amount of organometallic compound present is sufficient to provide a ratio of millimoles of organometallic compound to grams of support-activator of from about 0.001:1 to about 2:1.  
     
     
         62 . The process of  claim 61  wherein said ratio is from about 0.1:1 to about 0.8:1.  
     
     
         63 . The process of  claim 37  further comprising calcining the support-activator at a temperature of from about 100 to about 800° C. for a period of from about 1 to about 600 minutes.  
     
     
         64 . The process of  claim 37  further comprising recovering the support-activator having the pre-catalyst impregnated therein from the liquid hydrocarbon.