Method to prepare ethylene copolymers

Abstract

Catalyst systems and methods for making and using the same. A method of polymerizing olefins to produce a polyolefin polymer with a multimodal composition distribution, includes contacting ethylene and a comonomer with a catalyst system. The catalyst system includes a first catalyst compound and a second catalyst compound that are co-supported to form a commonly supported catalyst system. The first catalyst compound includes a compound with the general formula (C5HaR1b)(C5HcR2d)HfX2. The second catalyst compound includes at least one of the following general formulas:In both catalyst systems, the R groups can be independently selected from any number of substituents, including, for example, H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group, among others.

1 - 44 . (canceled) 
     
     
         45 . A catalyst composition comprising a first catalyst compound and a second catalyst compound that are co-supported forming a commonly supported catalyst system, wherein the first catalyst compound comprises the following formula: 
       
         
           
             
               
                 
                   Cp 
                 
                 A 
               
               
                 A 
               
               
                 
                   Cp 
                 
                 B 
               
               
                 
                   HfX 
                 
                 2 
               
             
           
         
       
       wherein each Cp A  and Cp B  can independently be selected from the group consisting of a cyclopentadienyl, a substituted cyclopentadienyl, an indenyl, a substituted indenyl, a fluorenyl or a substituted fluorenyl selected from the group consisting of one or more of a heteroatom and one or more of a group R, wherein the R group is selected from the group consisting of a hydrocarbyl or a substituted hydrocarbyl, wherein the substituted cyclopentadienyl for Cp A  is (C 5 H 3 R 1 ) and for Cp B  is (C 5 H 3 R 2 ), wherein each of R 1  and R 2  are independently a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; and each X is independently a leaving group selected from a divalent radical that links to an R 1  or R 2  group; and A is at least one of a bridging group selected from a divalent hydrocarbon, a divalent hydrocarbon containing at least one Group 13 to 16 atom or a combination thereof; and the second catalyst compound comprises at least one of the following formulas: 
       
         
           
           
               
               
           
         
       
       
         
           
           
               
               
           
         
       
        wherein each R 3  is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; R 4  is a hydrocarbyl group, a substituted hydrocarbyl group, or a heteoatom group; each R 5  is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; wherein R 3 , R 4 , and R 5  may be the same or different; wherein R 3 , R 4 , or R 5  groups may be joined with R 3 , R 4 , or R 5  groups on an opposing cyclopentadienyl structure to form one or more bridges if the number of atoms connecting the two cyclopentadienyl rings is > 3; and each X is independently a leaving group selected from a labile hydrocarbyl, a substituted hydrocarbyl, a heteroatom group, or a divalent radical that links to a R 3 , R 4 , or R 5  substituent. 
     
     
         46 . The catalyst composition of  claim 45 , wherein the least one Group 13 to 16 atom are selected from carbon, oxygen, nitrogen, silicon, aluminum, boron, germanium, tin and combinations thereof. 
     
     
         47 . The catalyst composition of  claim 45 , wherein the at least one bridging group is selected from a C 1  to C 6  alkylene, a substituted C 1  to C 6  alkylene, R′ 2 C<, R′ 2 Si<, >Si(R′) 2 Si(R′  2  )<, R′ 2 Ge<, and R′P<, wherein R′ is independently selected from the group consisting of a hydride, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, substituted halocarbyl, a hydrocarbyl-substituted organometalloid, a halocarbyl-substituted organometalloid, disubstituted boron, a disubstituted Group 15 atom, a substituted Group 16 atom and a halogen radical. 
     
     
         48 . The catalyst composition of  claim 47 , wherein two or more R′ form a ring. 
     
     
         49 . The catalyst composition of  claim 45 , wherein the at least one bridging group is selected from a divalent C 1  to C 20  hydrocarbyls and C 1  to C 20  hydrocarbonyls containing one to three heteroatoms. 
     
     
         50 . The catalyst composition of  claim 45 , wherein the at least one bridging group is a cyclic structure having 4 to 10 ring members. 
     
     
         51 . The catalyst composition of  claim 45 , wherein the second catalyst compound comprises at least one compound with the following formula: 
       
         
           
           
               
               
           
         
       
       
         
           
           
               
               
           
         
       
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         52 . The catalyst composition of  claim 45 , wherein the second catalyst compound comprises at least one compound with the following formula: 
       
         
           
           
               
               
           
         
       
       
         
           
           
               
               
           
         
       
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         53 . The catalyst composition of  claim 45 , wherein the second catalyst compound comprises at least one compound with the following formula:
                                             wherein each R 4A  is independently a methyl, ethyl, propyl, pentyl, hexyl, octyl, nonyl, dodecyl, phenethyl, or other hydrocarbyl.   
     
     
         54 . The catalyst composition of  claim 45 , wherein the second catalyst compound comprises at least one compound with the following formula: 
       
         
           
           
               
               
           
         
       
       
         
           
           
               
               
           
         
       
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         55 . The catalyst composition of  claim 45 , wherein the second catalyst compound comprises at least one compound with the following formula: 
       
         
           
           
               
               
           
         
       
       
         
           
           
               
               
           
         
       
       . 
     
     
         56 . The catalyst composition of  claim 45 , wherein the ratio of the first catalyst compound to the second catalyst compound is between about 10:1 to 1:10. 
     
     
         57 . The catalyst composition of  claim 45 , wherein the ratio of the first catalyst compound to the second catalyst compound is between about 3:1 to 1:3. 
     
     
         58 . The catalyst composition of  claim 45 , comprising an activator comprising an acid derived from a weakly coordinating anion. 
     
     
         59 . The catalyst composition of  claim 58 , wherein the activator comprises an aluminoxane compound, an organoboron, an organoaluminum compound or combinations thereof. 
     
     
         60 . The catalyst composition of  claim 58 , wherein the activator comprises methyl aluminoxane or modified methylauminoxane. 
     
     
         61 . The catalyst composition of  claim 59 , wherein the organoboron compound comprises BAr a R b , or AlAr a R b , wherein a+b = 3, a ≥2, and Ar is an aryl or heteroaryl group comprising a substituent containing fluorine and wherein R is independently H, a hydrocarbyl group, a substituted hydrocarbyl group or a heteroatom group. 
     
     
         62 . The catalyst composition of  claim 61 , wherein Ar is C 6 F 5 , C 10 F 7 , or C 6 H 3 (CF 3 ) 2 . 
     
     
         63 . The catalyst composition of  claim 45 , comprising a support comprising a mineral, a clay, a metal oxide, a metalloid oxide, a mixed metal oxide, a mixed metalloid oxide, a mixed metal-metalloid oxide, a polymer, or any combinations thereof. 
     
     
         64 . The catalyst composition of  claim 63 , wherein the support has been thermally treated and/or chemically treated with an acid, an organosilane, an organoaluminum, or a fluoriding agent, or any combinations thereof.