US 11,053,329 B2
Multiple non-coordinating anion activators for propylene-ethylene-diene monomer polymerization reactions
Rhutesh K. Shah, Katy, TX (US); Jo Ann M. Canich, Houston, TX (US); and Edward J. Blok, Huffman, TX (US)
Assigned to ExxonMobil Chemical Patents Inc., Baytown, TX (US)
Filed by ExxonMobil Chemical Patents Inc., Baytown, TX (US)
Filed on Mar. 18, 2019, as Appl. No. 16/356,826.
Claims priority of provisional application 62/644,971, filed on Mar. 19, 2018.
Prior Publication US 2019/0284319 A1, Sep. 19, 2019
Int. Cl. C08F 4/6592 (2006.01); C08F 236/20 (2006.01); C08F 4/643 (2006.01); C08F 4/659 (2006.01); C08F 4/649 (2006.01); C08F 2/38 (2006.01); C08F 210/18 (2006.01); C08F 210/16 (2006.01); C08J 3/24 (2006.01); C09J 123/16 (2006.01); B60C 1/00 (2006.01); C08L 23/16 (2006.01)
CPC C08F 4/6592 (2013.01) [C08F 2/38 (2013.01); C08F 4/6495 (2013.01); C08F 4/65908 (2013.01); C08F 4/65912 (2013.01); C08F 210/16 (2013.01); C08F 210/18 (2013.01); C08F 236/20 (2013.01); C08J 3/24 (2013.01); C09J 123/16 (2013.01); B60C 1/00 (2013.01); B60C 1/0016 (2013.01); C08F 2420/01 (2013.01); C08F 2420/02 (2013.01); C08F 2500/16 (2013.01); C08F 2800/10 (2013.01); C08F 2810/20 (2013.01); C08L 23/16 (2013.01)] 58 Claims
1. A method comprising:
1) contacting a catalyst system with an olefinic feed comprising a C3-C40 alpha olefin, ethylene, and a diene monomer under polymerization reaction conditions where the C3-C40 alpha olefin is present in the olefinic feed in a molar excess relative to a combined molar amount of the ethylene and the diene monomer, the catalyst system comprising a first non-coordinating anion activator, a second non-coordinating anion activator differing from the first non-coordinating anion activator, and a transition metal complex represented by the formula:
M is a group 3, 4, 5, or 6 transition metal;
Cp′ is an optionally substituted tetrahydro-s-indacenyl or tetrahydro-as-indacenyl group;
G is a heteroatom containing group having a formula of JR′z-y;
wherein J is N, P, O or S, R′ is a C1 to C100 optionally substituted hydrocarbyl, halocarbyl, silylcarbyl, or germylcarbyl group, and z is 2 when J is N or P, and z is 1 when J is O or S;
T is a bridging group and y is 0 or 1 indicating an absence (y=0) or a presence (y=1) of T, wherein when y is 1 Cp′ and G are bonded to the bridging group;
each X is, independently, a leaving group, or two Xs are joined and bound to the metal atom to form a metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene;
n=1, 2 or 3;
q=1, 2 or 3;
wherein a sum of m+n+q is equal to the oxidation state of M; and
2) obtaining a copolymer comprising 1 to 35 mol. % ethylene, 98.9 to 65 mol. % C3-C40 olefin, and 0.1 to 10 mol. % diene monomer having an MFR of 30 g/10 min or below,
wherein the first non-coordinating anion activator and the second non-coordinating anion activator interact synergistically under the polymerization reaction conditions such that melt flow rate of the copolymer changes non-linearly as a function of molar ratio of the first non-coordinating anion activator to the second non-coordinating anion activator, when measured under same polymerization conditions, except for having different activator ratios.