US 9,809,667 B2
Producing polyolefin products
Ching-Tai Lue, Sugar Land, TX (US); Francis C. Rix, League City, TX (US); C. Jeff Harlan, Houston, TX (US); and Laughlin G. McCullough, League City, TX (US)
Assigned to Univation Technologies, LLC, Houston, TX (US)
Appl. No. 15/116,696
Filed by Univation Technologies, LLC, Houston, TX (US)
PCT Filed Feb. 10, 2015, PCT No. PCT/US2015/015125
§ 371(c)(1), (2) Date Aug. 4, 2016,
PCT Pub. No. WO2015/123168, PCT Pub. Date Aug. 20, 2015.
Claims priority of provisional application 61/938,472, filed on Feb. 11, 2014.
Claims priority of provisional application 61/938,466, filed on Feb. 11, 2014.
Claims priority of provisional application 61/981,291, filed on Apr. 18, 2014.
Claims priority of provisional application 61/985,151, filed on Apr. 28, 2014.
Claims priority of provisional application 62/032,383, filed on Aug. 1, 2014.
Claims priority of provisional application 62/088,196, filed on Dec. 5, 2014.
Claims priority of provisional application 62/087,905, filed on Dec. 5, 2014.
Claims priority of provisional application 62/087,911, filed on Dec. 5, 2014.
Claims priority of provisional application 62/087,914, filed on Dec. 5, 2014.
Prior Publication US 2016/0347889 A1, Dec. 1, 2016
Int. Cl. C08F 4/653 (2006.01); C08F 4/6592 (2006.01); C08F 210/16 (2006.01); C08L 23/08 (2006.01); C08F 4/659 (2006.01); C07F 17/00 (2006.01); C08F 210/02 (2006.01); C08F 4/76 (2006.01)
CPC C08F 210/16 (2013.01) [C07F 17/00 (2013.01); C08F 4/65904 (2013.01); C08F 4/76 (2013.01); C08F 210/02 (2013.01); C08F 4/65912 (2013.01); C08F 4/65916 (2013.01); C08F 4/65925 (2013.01); C08F 4/65927 (2013.01); C08F 2410/02 (2013.01); C08F 2420/00 (2013.01); C08F 2500/01 (2013.01); C08F 2500/02 (2013.01); C08F 2500/08 (2013.01); C08F 2500/09 (2013.01); C08F 2500/10 (2013.01); C08F 2500/11 (2013.01); C08F 2500/12 (2013.01); C08F 2500/13 (2013.01); C08F 2500/18 (2013.01); C08F 2800/20 (2013.01); C08L 23/0815 (2013.01)] 20 Claims
 
1. A method of polymerizing olefins to produce a polyolefin polymer with a multimodal composition distribution, comprising contacting ethylene and a comonomer with a catalyst system, wherein the catalyst system comprises a first catalyst compound and a second catalyst compound that are co-supported to form a commonly supported catalyst system, wherein the first catalyst compound comprises the following formula:
(C5HaR1b)(C5HcR2d)HfX2
wherein each R1 is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; each R2 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 R1 and at least one R2 is a hydrocarbyl or substituted hydrocarbyl group; adjacent groups R1 and R2 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 R1 or R2 group; and the second catalyst compound comprises the following formula:

OG Complex Work Unit Drawing
wherein each R3 is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; R4 is a hydrocarbyl group, a substituted hydrocarbyl group, or a heteoatom group; each R5 is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; wherein R3, R4, and R5 are the same or different; 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 an R3, R4, or R5 group.