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 (C 5 H a R 1 b )(C 5 H c R 2 d )HfX 2 . 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 - 16 . (canceled) 
     
     
         17 . 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:
   (C 5 H a R 1   b )(C 5 H c R 2   d )HfX 2      
       wherein each R 1  is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; each R 2  is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; a and c are ≥3; a+b=c+d=5; at least one R 1  and at least one R 2  is a hydrocarbyl or substituted hydrocarbyl group; adjacent groups R 1  and R 2  groups are optionally coupled to form a ring; and each X is independently a leaving group selected from a labile hydrocarbyl, substituted hydrocarbyl, or heteroatom group, or a divalent radical that links to an R 1  or R 2  group; 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 heteroatom 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  are optionally the same or different; wherein R 3 , R 4 , or R 5  groups are joined with R 3  , R 4 , or R 5  groups on an opposing indenyl ring to form one bridge where the number of bridge atoms connecting the two indenyl 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; and
 wherein the catalyst composition further includes at least one Group 15 containing catalyst compound represented by the formula: 
 
       
         
           
           
               
               
           
         
       
       wherein:
 M is a Group 4, 5, or 6 metal; 
 y is 0 or 1, wherein when y is 0, group L′ is absent 
 n is the oxidation state of M; 
 m is the formal charge of the ligand represented by YZL and YZL′; L, L′, Y and Z are each a Group 15 element; 
 each R 11  and R 12  is independently a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; R 13  is absent or is H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; each R 14  and R 15  is independently a hydrocarbyl 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; each R 16  and R 17  is independently a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; and R* is absent, or is hydrogen, a Group 14 atom containing group, a halogen, or a heteroatom containing group. 
 
     
     
         18 - 21 . (canceled) 
     
     
         22 . The catalyst composition of  claim 17 , wherein the second catalyst compound comprises at least one compound with the following formula: 
       
         
           
           
               
               
           
         
       
     
     
         23 . The catalyst composition of  claim 17 , wherein the mole ratio of the first catalyst compound to the second catalyst compound is between about 10:1 to 1:10. 
     
     
         24 . The catalyst composition of  claim 17 , wherein the mole ratio of the first catalyst compound to the second catalyst compound is between about 3:1 to 1:3. 
     
     
         25 . The catalyst composition of  claim 17 , comprising an activator comprising an acid from a non-coordinating anion. 
     
     
         26 . The catalyst composition of  claim 25 , wherein the activator comprises an aluminoxane compound, an organoboron, an organoaluminum compound or combinations thereof 
     
     
         27 . The catalyst composition of  claim 25 , wherein the activator comprises methyl aluminoxane or modified methylauminoxane. 
     
     
         28 - 29 . (canceled) 
     
     
         30 . The catalyst composition of  claim 25 , wherein the weakly coordinating anion comprises BAr c R d -, or AlAr c R d -, or both, wherein c+d=4, c≥2, and Ar is an aryl or heteroaryl group comprising a substituent containing fluorine, and R d  is a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group. 
     
     
         31 . (canceled) 
     
     
         32 . The catalyst composition of  claim 17 , 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. 
     
     
         33 . The catalyst composition of  claim 32 , wherein the support is a polyolefin or a polyolefin derivative. 
     
     
         34 . The catalyst composition of  claim 32 , 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. 
     
     
         35 - 36 . (canceled) 
     
     
         37 . The catalyst composition of  claim 17 , comprising a silica support and a methyl aluminoxane activator. 
     
     
         38 - 39 . (canceled) 
     
     
         40 . The catalyst composition of  claim 17 , wherein the catalyst composition further includes a third catalyst compound comprising an inorganic or organometallic complexes of a lanthanide, an actinide, Ti, Zr, Hf, V, Cr, Fe, Ru, Co, Rh, Ni, or Pd. 
     
     
         41 . The catalyst composition of  claim 17 , wherein the catalyst composition further includes a third catalyst compound comprising a formula of Cp A (A)Cp B M′X′ n , Cp A (A)QM′X′ n  or Cp A M′Q q X′ n , wherein Cp A  and Cp B  may each be independently a cyclopentadienyl ligand, or a ligands isolobal to cyclopentadienyl, either or both Cp A  and Cp B  may contain heteroatoms, and either or both Cp A  and Cp B  are optionally substituted by one or more R 8  groups, wherein M′ is selected from the group consisting of Groups 3 through 12 atoms and lanthanide Group atoms, wherein X′ is an anionic leaving group, wherein n is 0 or an integer from 1 to 4, wherein A is selected from the group consisting of divalent alkyls, divalent lower alkyls, divalent substituted alkyls, divalent heteroalkyls, divalent alkenyls, divalent lower alkenyls, divalent substituted alkenyls, divalent heteroalkenyls, divalent alkynyls, divalent lower alkynyls, divalent substituted alkynyls, divalent heteroalkynyls, divalent alkoxys, divalent lower alkoxys, divalent aryloxys, divalent alkylthios, divalent lower alkyl thios, divalent arylthios, divalent aryls, divalent substituted aryls, divalent heteroaryls, divalent aralkyls, divalent aralkylenes, divalent alkaryls, divalent alkarylenes, divalent haloalkyls, divalent haloalkenyls, divalent haloalkynyls, divalent heteroalkyls, divalent heterocycles, divalent heteroaryls, divalent heteroatom-containing groups, divalent hydrocarbyls, divalent lower hydrocarbyls, divalent substituted hydrocarbyls, divalent heterohydrocarbyls, divalent silyls, divalent boryls, divalent phosphinos, divalent phosphines, divalent aminos, divalent amines, divalent ethers, divalent thioethers; wherein the R 8  groups are selected from the group consisting of alkyls, lower alkyls, substituted alkyls, heteroalkyls, alkenyls, lower alkenyls, substituted alkenyls, heteroalkenyls, alkynyls, lower alkynyls, substituted alkynyls, heteroalkynyls, alkoxys, lower alkoxys, aryloxys, alkylthios, lower alkyl thios, arylthios, aryls, substituted aryls, heteroaryls, aralkyls, aralkylenes, alkaryls, alkarylenes, haloalkyls, haloalkenyls, haloalkynyls, heteroalkyls, heterocycles, heteroaryls, heteroatom-containing groups, hydrocarbyls, lower hydrocarbyls, substituted hydrocarbyls, heterohydrocarbyls, silyls, boryls, phosphinos, phosphines, aminos, amines, ethers, thioethers wherein Q is selected from the group consisting of heteroatom-containing ligands, ROO—, RO—, R(O)—, —NR—, —CR 2 —, —S—, —NR 2 , —CR 3 , —SR, —SiR 3 , —PR 2 , —H, and substituted and unsubstituted aryl groups; and wherein q is selected from 0 to 3. 
     
     
         42 - 44 . (canceled)