US 12,146,020 B2
Hybrid supported metallocene catalyst and process for preparing polyethylene copolymer using the same
Hyun Jee Kwon, Daejeon (KR); Seungmi Lee, Daejeon (KR); Jung Won Lee, Daejeon (KR); Poeun Kim, Daejeon (KR); Yongwoo Kwon, Daejeon (KR); and Ki Soo Lee, Daejeon (KR)
Assigned to LG Chem, Ltd., Seoul (KR)
Appl. No. 17/601,281
Filed by LG Chem, Ltd., Seoul (KR)
PCT Filed Sep. 29, 2020, PCT No. PCT/KR2020/013426
§ 371(c)(1), (2) Date Oct. 4, 2021,
PCT Pub. No. WO2021/066579, PCT Pub. Date Apr. 8, 2021.
Claims priority of application No. 10-2019-0120944 (KR), filed on Sep. 30, 2019; and application No. 10-2020-0126247 (KR), filed on Sep. 28, 2020.
Prior Publication US 2022/0162353 A1, May 26, 2022
Int. Cl. C08F 4/6592 (2006.01); C08F 210/02 (2006.01)
CPC C08F 4/6592 (2013.01) [C08F 210/02 (2013.01)] 18 Claims
 
1. A hybrid supported metallocene catalyst, comprising at least one first metallocene compound selected from compounds represented by the following Chemical Formula 1; at least one second metallocene compound selected from compounds represented by the following Chemical Formula 2; and a support on which the first and the second metallocene compounds are supported:

OG Complex Work Unit Chemistry
in Chemical Formula 1,
M1 is a Group 4 transition metal;
A is carbon (C), silicon (Si), or germanium (Ge);
X1 and X2 are the same as or different from each other, and are each independently halogen, a nitro group, an amido group, a phosphine group, a phosphide group, a C1 to C30 hydrocarbyl group, a C1 to C30 hydrocarbyloxy group, a C2 to C30 hydrocarbyloxyhydrocarbyl group, —SiH3, a C1 to C30 hydrocarbyl (oxy) silyl group, a C1 to C30 sulfonate group, or a C1 to C30 sulfone group;
R1 and R3 to R10 are the same as or different from each other, and are each independently hydrogen, a C1 to C30 hydrocarbyl group, a C1 to C30 hydrocarbyloxy group, or a C2 to C30 hydrocarbyloxyhydrocarbyl group;
R2 is hydrogen, a C1 to C30 hydrocarbyl group, a C1 to C30 hydrocarbyloxy group, a C2 to C30 hydrocarbyloxyhydrocarbyl group, a C1 to C20 hydrocarbyl (oxy) silyl group, or a Cl to C20 silylhydrocarbyl group; and
Q1 and Q2 are the same as or different from each other, and are each independently a C1 to C30 hydrocarbyl group, or a C1 to C30 hydrocarbyloxy group;

OG Complex Work Unit Chemistry
in Chemical Formula 2,
M2 is a Group 4 transition metal;
X3 and X4 are the same as or different from each other, and are each independently halogen, a nitro group, an amido group, a phosphine group, a phosphide group, a C1 to C30 hydrocarbyl group, a C1 to C30 hydrocarbyloxy group, a C2 to C30 hydrocarbyloxyhydrocarbyl group, —SiH3, a C1 to C30 hydrocarbyl (oxy) silyl group, a Cl to C30 sulfonate group, or a C1 to C30 sulfone group;
Z is —O—, —S—, —NRa—, or —PRa—;
Ra is hydrogen, a C1 to C20 hydrocarbyl group, a C1 to C20 hydrocarbyl (oxy) silyl group, or a C1 to C20 silylhydrocarbyl group;
T is

OG Complex Work Unit Chemistry
T1 is C, Si, Ge, Sn, or Pb;
Q3 is hydrogen, a C1 to C30 hydrocarbyl group, a C1 to C30 hydrocarbyloxy group, a C2 to C30 hydrocarbyloxyhydrocarbyl group, —SiH3, a C1 to C30 hydrocarbyl (oxy) silyl group, a C1 to C30 hydrocarbyl group substituted with halogen, or —NRbRc;
Q4 is a C2 to C30 hydrocarbyloxyhydrocarbyl group;
Rb and Rc are each independently hydrogen, or a C1 to C30 hydrocarbyl group, or Rb and Rc are connected with each other, and together with N to which they are attached to form an aliphatic or aromatic ring; and
C1 is any one of ligands represented by the following Chemical Formulae 2a to 2d,

OG Complex Work Unit Chemistry
in Chemical Formulae 2a to 2d,
Y is O, or S,
R11 to R16 are the same as or different from each other, and are each independently hydrogen, a C1 to C30 hydrocarbyl group, or a C1 to C30 hydrocarbyloxy group;
custom characterrepresents a site of binding to T, and
custom characterrepresents a site of binding to M2.