Supported catalyst systems and processes for use thereof

Patent metadata

Field	Value
Publication number	US-11738334-B2
Application number	US-202117165618-A
Country	US
Kind code	B2
Filing date	Feb 2, 2021
Priority date	Aug 11, 2020
Publication date	Aug 29, 2023
Grant date	Aug 29, 2023

Abstract

This invention relates to a supported catalyst system comprising: (i) at least one first catalyst component comprising a group 4 bis(phenolate) complex; (ii) at least one second catalyst component comprising a 2,6-bis(imino)pyridyl iron complex; (iii) activator; and (iv) support. The catalyst system may be used for preparing polyolefins, such a bimodal polyethylene, typically in a gas phase polymerization.

First claim

What is claimed is:

1. A supported catalyst system comprising: (i) at least one first catalyst a component comprising a tridentate complex; (ii) at least one second catalyst component comprising a 2,6-bis(imino)pyridyl iron complex; (iii) activator; and (iv) support; wherein,
a tridentate complex is represented by Formula (A):

wherein:
M is a group 3-6 transition metal or Lanthanide;
E and E′ are each independently O, S, or NR 9 , where R 9 is independently hydrogen, C 1 -C 40 hydrocarbyl, C 1 -C 40 substituted hydrocarbyl, or a heteroatom-containing group;
a Q is group 15, or 16 atom that forms a dative bond to metal M;
A 1 QA 1′ are part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms that links A 2 to A 2′ via a 3-atom bridge with Q being the central atom of the 3-atom bridge, A 1 and A 1′ are independently C, N, or C(R 22 ), where R 22 is selected from hydrogen, C 1 -C 20 hydrocarbyl, C 1 -C 20 substituted hydrocarbyl;
A 3 A 2 is a divalent group containing 2 to 40 non-hydrogen atoms that links A 1 to the E-bonded aryl group via a 2-atom bridge;
A 2′ A 3′ is a divalent group containing 2 to 40 non-hydrogen atoms that links A 1′ to the E′-bonded aryl group via a 2-atom bridge;
L is a neutral Lewis base;
X is an anionic ligand;
n is 1, 2 or 3;
m is 0, 1, or 2;
n+m is not greater than 4;
each of R 1* , R 2* , R 3* , R 4* , R 1′ , R 2′ , R 3′ , and R 4′ is independently hydrogen, C 1 -C 40 hydrocarbyl, C 1 -C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more of R 1* and R 2* , R 2* and R 3* , R 3* and R 4* , R 1′ and R 2′ , R 2′ and R 3′ , R 3′ and R 4′ are optionally joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms, and where substitutions on the ring optionally join to form additional rings;
any two L groups are optionally joined together to form a bidentate Lewis base;
an X group is optionally joined to an L group to form a monoanionic bidentate group;
any two X groups are optionally joined together to form a dianionic ligand group; and

the 2,6-bis(imino)pyridyl iron complex is represented by Formula (I):

wherein:
each of R 1 and R 2 is independently hydrogen, C 1 -C 22 alkyl, C 2 -C 22 alkenyl, C 6 -C 22 aryl, arylalkyl wherein alkyl has from 1 carbon atom to 10 carbon atoms and aryl has from 6 carbon atoms to 20 carbon atoms, or five-, or six-, or seven-membered heterocyclic ring comprising at least one atom selected from the group consisting of N, P, O and S; wherein each of R 1 and R 2 is optionally substituted by halogen, —OR 16 , —NR 17 2 , or —SiR 18 3 ; wherein R 1 optionally bonds with R 3 , and R 2 optionally bonds with R 5 , in each case to independently form a five-, six-, or seven-membered ring;
each of R 3 , R 4 , R 5 , R 8 , R 9 , R 10 , R 13 , R 14 , and R 15 is independently hydrogen, C 1 -C 22 alkyl, C 2 -C 22 alkenyl, C 6 -C 22 aryl, arylalkyl wherein alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, —OR 16 , —NR 17 2 , halogen, —SiR 18 3 or five-, six- or seven-membered heterocyclic ring comprising at least one atom selected from the group consisting of N, P, O and S;
wherein R 3 , R 4 , R 5 , R 8 , R 9 , R 10 , R 13 , R 14 , and R 15 are optionally substituted by halogen, —OR 16 , —NR 17 2 or —SiR 18 3 ; wherein R 3 optionally bonds with R 4 , R 4 optionally bonds with R 5 , R 7 optionally bonds with R 10 , R 10 optionally bonds with R 9 , R 9 optionally bonds with R 8 , R 8 optionally bonds with R 6 , R 15 optionally bonds with R 14 , R 14 optionally bonds with R 13 , and R 13 optionally bonds with R 11 , in each case to independently form a five-, six- or seven-membered carbocyclic or heterocyclic ring, the heterocyclic ring comprising at least one atom from the group consisting of N, P, O and S;
each of R 6 , R 7 , R 11 , and R 12 is independently hydrogen, C 1 -C 22 alkyl, C 2 -C 22 alkenyl, C 6 -C 22 aryl, arylalkyl wherein alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, a heteroatom or a heteroatom-containing group; wherein R 6 , R 7 , R 11 , and R 12 are optionally substituted by halogen, —OR 16 , —NR 17 2 or —SiR 18 3 , wherein R 6 optionally bonds with R 8 , R 11 optionally bonds with R 13 , or R 15 optionally bonds with R 12 in each case to independently form a five-, six- or seven-membered carbocyclic or heterocyclic ring, the heterocyclic ring comprising at least one atom from the group consisting of N, P, O and S; wherein at least one of R 6 , R 7 , R 11 , and R 12 is independently a heteroatom or a heteroatom-containing group, or at least one of the R 6 , R 7 , R 11 , and R 12 is not methyl, or when R 11 is H and R 12 is iPr, then at least one of R 6 and R 7 is not methyl;
each of R 16 , R 17 , and R 18 is independently hydrogen, C 1 -C 22 alkyl, C 2 -C 22 alkenyl, C 6 -C 22 aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, or —SiR 19 3 , wherein each R 16 , R 17 , and R 18 is independently optionally substituted by halogen, or two R 16 radicals optionally bond to form a five- or six-membered ring, or two R 17 radicals optionally bond to form a five- or six-membered ring, or two R 18 radicals optionally bond to form a five- or six-membered ring;
each R 19 is independently hydrogen, C 1 -C 22 alkyl, C 2 -C 22 alkenyl, C 6 -C 22 aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, or two R 19 radicals optionally bond to form a five- or six-membered ring;
each of E 1 , E 2 , and E 3 is independently carbon, nitrogen or phosphorus;
each of u 1 , u 2 , and u 3 is independently 0 when E 1 , E 2 , or E 3 is nitrogen or phosphorus, and each of u 1 , u 2 , and u 3 is independently 1 when E 1 , E 2 , or E 3 is carbon;
each of X 1 and X 2 is independently a substituted hydrocarbyl, and the radicals X are optionally bonded with one another;
r is 1 or 2;
s is 1 or 2;
D is a neutral donor; and
t is 0 to 2.

2. The supported catalyst system of claim 1 , wherein the tridentate complex is represented by the Formula (A-II):

wherein:
M is a group 3, 4, 5, or 6 transition metal or a Lanthanide;
E and E′ are each independently O, S, or NR 9 *, where R 9 * is independently hydrogen, C 1 -C 40 hydrocarbyl, C 1 -C 40 substituted hydrocarbyl, or a heteroatom-containing group;
each L is independently a Lewis base;
each X is independently an anionic ligand;
n is 1, 2 or 3;
m is 0, 1, or 2;
n+m is not greater than 4;
each of R 1* , R 2* , R 3* , R 4* , R 1′ , R 2′ , R 3′ , and R 4′ is independently hydrogen, C 1 -C 40 hydrocarbyl, C 1 -C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more of R 1* and R 2* , R 2* and R 3* , R 3* and R 4* , R 1′ and R 2′ , R 2′ and R 3′ , R 3′ and R 4′ are optionally joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms, and where substitutions on the ring optionally join to form additional rings;
any two L groups are optionally joined together to form a bidentate Lewis base;
an X group is optionally joined to an L group to form a monoanionic bidentate group;
any two X groups are optionally joined together to form a

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Holtcamp Matthew W
• Li Dongming
• Stevens Kevin A
• Canich Jo Ann M
• Hagadorn John R
• Mathialagan Ramyaa
• Boller Timothy M

Classifications

• B01J31/2243 Primary

  At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand · CPC title

• B01J21/08

  Silica · CPC title

• B01J31/1616

  Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts (catalysts comprising molecular sieves B01J29/00) · CPC title

• C08F4/646

  Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64 {(C08F4/64003 - C08F4/64196 take precedence)} · CPC title

• C08F4/64124

  ONO · CPC title