Mixed Catalyst Systems Containing Iron Tridentate Carbenes and Methods for Making Polymer Products Using Same

A process for the production of an ethylene alpha-olefin copolymer comprising:

• polymerizing ethylene and at least one C3-C20 alpha-olefin by contacting the ethylene and the at least one C3-C20 alpha-olefin with a mixed catalyst system comprising at least one activator, a first catalyst compound, and a second catalyst compound different from the first catalyst compound, the polymerizing occurring in at least one gas phase reactor or at least one slurry phase at a reactor pressure of from 0.7 to 70 bar and a reactor temperature from 20° C. to 150° C. to form an ethylene alpha-olefin copolymer,
• the first catalyst compound represented by Formula (I):
• wherein:
• each of R1, R2, R3, R4, R5, R6, R9, R10, R11, R12, R13, R14, R15, R16, R17, and R18 is independently hydrogen, C1-C22-alkyl, C2-C22-alkenyl, C6-C22-aryl, arylalkyl wherein alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, alkylaryl wherein alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, —NR′2, —OR′, halogen, —NO2, —SiR′3, or five-, six-, or seven-membered heterocyclyl comprising at least one atom selected from N, P, O, and S, wherein R1, R2, R3, R4, R5, R6, R9, R10, R11, R12, R13, R14, R15, R16, R17, and R18 are optionally substituted by halogen, —NO2, —CF3, —CF2CF3, —CH2CF3, —NR′2, —OR′, or —SiR″3, wherein each R′ is independently hydrogen, C1-C22-alkyl, C2-C22-alkenyl, C6-C22-aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, or —SiR″3, wherein R′ is optionally substituted by halogen, or two R′ radicals optionally bond to form a five- or six-membered ring, wherein each R″ is independently hydrogen, C1-C22-alkyl, C2-C22-alkenyl, C6-C22-aryl, arylalkyl wherein alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, or two R″ radicals optionally bond to form a five- or six-membered ring;
• each of R1 and R8 is independently hydrogen, C1-C22-alkyl, C2-C22-alkenyl, C6-C22-aryl, arylalkyl wherein alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, or five-, six-, or seven-membered heterocyclyl comprising at least one atom selected from N, P, O, and S, wherein each of R7 and R8 is optionally substituted by halogen, —NR′2, —OR′, or —SiR″3, wherein R7 optionally bonds with R5 or R6, and R8 optionally bonds with R1 or R2, in each case to independently form a five-, six- or seven-membered ring;
• each of E1, E2, and E3 is independently carbon, nitrogen, or phosphorus;
• u is 1 for R1u and R2u if E1 is carbon, u is 1 for R3u and R4u if E2 is carbon, and u is 1 for R5u and R6u if E3 is carbon;
• u is 0 for R2u and 1 for R1u if E1 is nitrogen or phosphorus, u is 0 for R4u and 1 for R3u if E2 is nitrogen or phosphorus, and u is 0 for R6u and 1 for R5u if E3 is nitrogen or phosphorus;
• each X is independently fluorine, chlorine, bromine, iodine, hydrogen, C1-C20-alkyl, C2-C10-alkenyl, C6-C20-aryl, arylalkyl wherein alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, —NR′″2, —OR′″, —SR′″, —SO3R′″, —OC(O)R′″, —CN, —SCN, 0-diketonate, —CO, —BF4, —PF6 or bulky non-coordinating anions, or the radicals X are bonded with one another, wherein each R′″ is independently hydrogen, C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, or —SiR″″3, wherein R′″can be substituted by halogen or nitrogen- or oxygen-containing groups or two R′″radicals optionally bond to form a five- or six-membered ring, wherein each R″″ is independently hydrogen, C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl or arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, wherein R″″ can be substituted by halogen or nitrogen- or oxygen-containing groups or two R″″ radicals optionally bond to form a five- or six-membered ring;
• s is 1, 2, or 3;
• D is a neutral donor;
• and
• t is 0, 1, or 2;
• the second catalyst compound represented by formula (IV):
• wherein:
• each of R1, R2, and R3 is independently hydrogen, C1-C22-alkyl, C2-C22-alkenyl, C6-C22-aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, alkylaryl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, —NR′2, —OR′, halogen, —NO2, —SiR″3 or five-, six-, or seven-membered heterocyclyl comprising at least one atom selected from N, P, O and S;
• wherein any one or more of R1, R2, and R3 are optionally substituted by halogen, —CF3, —CF2CF3, —CH2CF3, —NO2, —NR′2, —OR′, or —SiR″3;
• wherein each R′ is independently hydrogen, C1-C22-alkyl, C2-C22-alkenyl, C6-C22-aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, or —SiR″3;
• wherein any one or more R′ radicals is optionally substituted by halogen, or two R′ radicals optionally bond to form a five- or six-membered ring;
• wherein each R″ is independently hydrogen, C1-C22-alkyl, C2-C22-alkenyl, C6-C22-aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms;
• wherein two R″ radicals optionally bond to form a five- or six-membered ring;
• each of R4 and R5 is independently C1-C22-alkyl, C2-C22-alkenyl, C6-C22-aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, or five-, six-, or seven-membered heterocyclyl comprising at least one atom selected from N, P, O, and S;
• wherein each of R4 and R5 is optionally individually substituted by halogen, —NR′2, —OR′, or —SiR″3;
• wherein R4 optionally bonds with R1, and/or wherein R5 optionally bonds with R3, in each case to independently form a five-, six- or seven-membered ring;
• each of R6 and R7 is independently C1-C22-alkyl, C2-C22-alkenyl, C6-C22-aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, alkylaryl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, —NR′2, —OR′, halogen, —NO2, —SiR″3 or five-, six-, or seven-membered heterocyclyl comprising at least one atom selected from N, P, O and S;
• wherein each of R4 and R5 is optionally individually substituted by halogen, —CF3, —CF2CF3, —CH2CF3, —NO2, —NR′2, —OR′, or —SiR″3;
• each X is independently fluorine, chlorine, bromine, iodine, hydrogen, C1-C20-alkyl, C2-C10-alkenyl, C6-C20-aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, —NR′″2, —OR′″, —SR′″, —SO3R′″, —OC(O)R′″, —CN, —SCN, β-diketonate, —CO, —BF4, —PF6—, or bulky non-coordinating anions, wherein X radicals are optionally bonded with one another;
• wherein each R′″ is independently hydrogen, C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, or —SiR″″3;
• wherein one or more R′″ is optionally substituted by halogen or nitrogen- or oxygen-containing groups, or two R′″radicals optionally bond to form a five- or six-membered ring;
• wherein each R″″ is independently hydrogen, C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl or arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms;
• wherein one or more R″″ is optionally substituted by halogen or nitrogen- or oxygen-containing groups, or two R″″ radicals optionally bond to form a five- or six-membered ring;
• s is 1, 2, or 3;
• D is a neutral donor;
• and
• t is 0, 1 or 2.