Bis-phenyl-phenoxy polyolefin procatalysts having two anthracenyl ligands

Abstract

Embodiments of this disclosure are directed to catalyst systems comprising a metal-ligand complex according to formula (I).

1 . A catalyst system comprising a metal-ligand complex according to formula (I): 
       
         
           
           
               
               
           
         
         where: 
         M is a metal chosen from titanium, zirconium, or hafnium, the metal being in a formal oxidation state of +2, +3, or +4; 
         n is 0, 1, or 2; 
         when n is 1, X is a monodentate ligand or a bidentate ligand; 
         when n is 2, each X is independently a monodentate ligand; 
         the metal-ligand complex is overall charge-neutral; 
         each Z is independently chosen from —O—, —S—, —N(R N )—, or —P(R P )—; 
         L is (C 2 -C 40 )hydrocarbylene or (C 2 -C 40 )heterohydrocarbylene; 
         R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10  are independently chosen from (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, —Si(R C ) 3 , —Ge(R C ) 3 , −P(R P ) 2 , —N(R N ) 2 , —N═CHR C , —OR C , —SR C , —NO 2 , —CN, —CF 3 , R C S(O)—, R C S(O) 2 —, (R C ) 2 C═N—, R C C(O)O—, R C OC(O)—, R C C(O)N(R N )—, (R C ) 2 NC(O)—, halogen, or —H, provided at least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10  is not —H, and wherein optionally any of R 1  and R 2 , or R 4  and R 5 , or R 6  and R 7 , or R 9  and R 10  may be covalently connected; 
         R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , and R 18  are independently chosen from (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, —Si(R C ) 3 , —Ge(R C ) 3 , —P(R P ) 2 , —N(R N ) 2 , —N═CHR C , —OR C , —SR C , —NO 2 , —CN, —CF 3 , R C S(O)—, R C S(O) 2 —, (R C ) 2 C═N—, R C C(O)O—, R C OC(O)—, R C C(O)N(R)—, (R C ) 2 NC(O)—, halogen, or —H; 
         each R C , R P , and R N  in formula (I) is independently a (C 1 -C 30 )hydrocarbyl or —H. 
       
     
     
         2 . (canceled) 
     
     
         3 . The catalyst system according to  claim 1 , wherein M is zirconium or hafnium. 
     
     
         4 . The catalyst system according to  claim 1 , wherein at least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10  is (C 3 -C 10 )alkyl, —Si(R C ) 3 , or —Ge(R C ) 3 . 
     
     
         5 . The catalyst system according to  claim 1 , wherein two of R 1 , R 2 , R 3 , R 4 , and R 5  are (C 3 -C 10 )alkyl, —Si(R C ) 3 , or —Ge(R C ) 3  and two of R 6 , R 7 , R 8 , R 9 , and R 10  are (C 3 -C 10 )alkyl, —Si(R C ) 3 , or —Ge(R C ) 3 . 
     
     
         6 . The catalyst system according to  claim 1 , wherein R 1  and R 5  are (C 3 -C 10 )alkyl, —Si(R C ) 3 , or —Ge(R C ) 3 . 
     
     
         7 . The catalyst system according to  claim 1 , wherein R 2  and R 7  are (C 3 -C 10 )alkyl, —Si(R C ) 3 , or —Ge(R C ) 3 . 
     
     
         8 . The catalyst system according to  claim 1 , wherein R 3  and R 8  are (C 3 -C 10 )alkyl, —Si(R C ) 3 , or —Ge(R C ) 3 . 
     
     
         9 . The catalyst system according to  claim 1 , wherein R 1 , R 4 , R 6 , and R 9  are independently (C 3 -C 10 )alkyl. 
     
     
         10 . The catalyst system according to  claim 1 , wherein R 1 , R 5 , R 6 , and R 10  are tert-butyl, and R 3 , R 4 , R 7 , R 8 , and R 9  are —H. 
     
     
         11 . The catalyst system according to  claim 1 , wherein R 1 , R 2 , R 9 , and R 10  are tert-butyl, and R 3 , R 4 , R 5 , R 6 , R 7 , and R 8  are —H. 
     
     
         12 . The catalyst system according to  claim 1 , wherein R 11  and R 18  are tert-octyl or n-octyl. 
     
     
         13 . The catalyst system according to  claim 1 , wherein R 12  and R 17  are halogen. 
     
     
         14 . The catalyst system according to  claim 1 , wherein R 11  and R 18  are methyl; and wherein R 12  and R 17  are halogen. 
     
     
         15 . The catalyst system according to  claim 1 , wherein R 14  and R 15  are methyl. 
     
     
         16 . The catalyst system according to  claim 1 , wherein R 9  and R 10  are covalently connected to form an optionally substituted 6-membered cycloalkyl ring; and R 1  and R 2  are covalently connected to form an optionally substituted 6-membered cycloalkyl ring. 
     
     
         17 . The catalyst system according to  claim 1  wherein R 1 , R 5 , R 9 , and R 10  are each —SiR C   3 , where R C  is methyl, ethyl or propyl. 
     
     
         18 . The catalyst system according to  claim 1 , wherein R 3  and R 8  are unsubstituted (C 1 -C 20 )aryl, substituted (C 1 -C 20 )aryl, or (C 1 -C 20 )heteroaryl. 
     
     
         19 . The catalyst system according to  claim 18 , wherein R 2  and R 9  are (C 1 -C 10 )alkyl. 
     
     
         20 . The catalyst system according to  claim 1 , wherein L is chosen from —CH 2 (CH 2 ) n CH 2 —, wherein n is 1 to 3, —CH 2 Si(R C ) 2 CH 2 , —CH 2 Ge(R C ) 2 CH 2 —, —CH(CH 3 )CH 2 CH(CH 3 )—, cyclohexane-1,2-diyldimethyl. 
     
     
         21 . A polymerization process comprising:
 polymerizing ethylene and one or more olefins in the presence of a catalyst system according to  claim 1 , under olefin polymerizing conditions to form an ethylene-based polymer.