Multi-metallic organometallic complexes, and related polymers, compositions, methods and systems

Patent metadata

Field	Value
Publication number	US-9233996-B2
Application number	US-201213615552-A
Country	US
Kind code	B2
Filing date	Sep 13, 2012
Priority date	Sep 13, 2011
Publication date	Jan 12, 2016
Grant date	Jan 12, 2016

Abstract

Multi-metallic organometallic complexes that allow performance of olefin based reaction and in particular polymerization of olefins to produce polyolefin polymers, and related methods and systems are described.

First claim

The invention claimed is:

1. A multi-metallic organometallic complex comprising:
a rigid base linker comprising a central ring formed by a monocyclic or bicyclic aromatic moiety or a spirane moiety, the central ring attaching two or more exterior rings, each of the two or more exterior rings attaching a metal-presenting arm, thus defining two or more metal-presenting arms in syn position with respect to the rigid base linker,

wherein:
each metal-presenting arm of said two or more metal-presenting arms comprises one or more ancillary ligands presenting said metal,
said metal is bound to one or more auxiliary ligands through respective one or more auxiliary ligand metal bonds,
each said one or more auxiliary ligand metal bonds is adapted to be represented through corresponding one or more auxiliary ligand metal bond three-dimensional vectors originating at said metal,
metals pertaining to different metal-presenting arms are located at a metal-to-metal distance defining an imaginary sphere having said metal-to-metal distance as a diameter, and
for each of said metals located at the metal-to-metal distance, a resulting vector corresponding to a sum of said one or more auxiliary ligand metal bond three-dimensional vectors is located inside said imaginary sphere; and
wherein the multi-metallic organometallic complex has formula I:

wherein,
n is between 0 and 4;
m1, m2, and m3 are independently between 1 and 4;
p1, p2, and p3 are independently between 1 and 4;
X is the monocyclic or bicyclic aromatic moiety or the spirane moiety;
Y1, Y2, and Y3 independently comprise an aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring;
L anc 1 , L anc 2 , and L anc 3 are independently selected from a monodentate or a multidentate ligand;
M 1 , M 2 , and M 3 are metals; and
L aux 1 , L aux 2 , L aux 3 are independently selected monodentate or a multidentate ligand.

2. The multi-metallic organometallic complex of claim 1 , wherein the two or more exterior rings are each connected to the central ring through a single bond.

3. The multi-metallic organometallic complex of claim 1 , wherein the central ring is a monocyclic or bicyclic heteroaromatic moiety or a heterospirane moiety and the two or more exterior rings independently comprise aromatic, heteroaromatic, aliphatic, or heteroaliphatic rings.

4. The multi-metallic organometallic complex of claim 1 , wherein X has the formula II, III, IV, V, VI, VII, or VIII:

wherein R1-R8 and R50-R57 are independently selected from the group consisting of N, C—H, C-alkyl, C-aryl, C-alkoxy, C-aryloxyl and a C attachment for Y1, Y2, Y3 or Y4; wherein at least one of R1-R8 and R50-57 in a corresponding ortho position with respect to Y1, and at least one of R1-R8 and R50-57 in a corresponding ortho position with respect to Y2 is not C—H, and at least one of R1-R8 and R50-57 in a corresponding ortho position with respect to Y3 is not C—H, and A is O, N—H, or S, and
wherein R58 and R59 are independently selected from the group consisting of H, alkyl, aryl, alkoxy, and aryloxyl.

5. The multi-metallic organometallic complex of claim 1 , wherein Y1, Y2, and Y3 have formula IX, X, XI, XII, or XIII:

in which
R10 to R26 are independently selected from the group consisting of H, linear C1-C15 alkyl; branched linear C3-C15 alkyl; cyclic C3-C15 alkyl; linear, cyclic, or branched C2-C15 alkenyl; linear, cyclic, or branched C2-C15 alkynyl; C6-C20 substituted or unsubstituted aryl; and C6-C20 substituted or unsubstituted heteroaryl;
wherein L anc 1 , L anc 2 , and L anc 3 comprise one or more ancillary ligands, independently selected from L anc a , L anc b , L anc b , L anc d , L anc e , and L anc f ;
wherein L anc a has the formula XIV, XV, XVI, or XVII:

wherein R27 is alkyl, aryl, heteroaryl, substituted aryl, R28-R37 and R39-44 are selected from the group consisting of H, linear C 1 -C15 alkyl; branched linear C3-C15 alkyl; cyclic C3-C15 alkyl; linear, cyclic, or branched C2-C15 alkenyl; linear, cyclic, or branched C2-C15 alkynyl; C6-C20 substituted or unsubstituted aryl; and C6-C20 substituted or unsubstituted heteroaryl; R38 is C or Si; Z═O, S, Se, or N;
L anc b comprises an O, N, or C;
L anc c comprises an O, N, or C; and
L anc d , L anc e , and L anc f are independently selected from the group consisting of:

6. The multi-metallic organometallic complex of claim 1 , wherein L anc 1 , L anc 2 , and L anc 3 comprise one or more ancillary ligands, independently selected from L anc a , L anc b , L anc c , L anc d , L anc e , and L anc f ,
wherein L anc a has the formula XIV, XV, XVI, or XVII:

wherein R27 is alkyl, aryl, heteroaryl, substituted aryl, R28-R37 and R39-44 are selected from the group consisting of H, linear C1-C15 alkyl; branched linear C3-C15 alkyl; cyclic C3-C15 alkyl; linear, cyclic, or branched C2-C15 alkenyl; linear, cyclic, or branched C2-C15 alkynyl; C6-C20 substituted or unsubstituted aryl; and C6-C20 substituted or unsubstituted heteroaryl; R38 is C or Si; Z═O, S, Se, or N;
L anc b comprises an O, N, or C;
L anc c comprises an O N, or C; and
L anc d , L anc e , and L anc f are independently selected from the group consisting of:

7. The multi-metallic organometallic complex of claim 1 , wherein L aux 1 , L aux 2 , and L aux 3 independently comprise an O, N, alkyl, aryl, amine, alkyloxide, aryloxide, or halogen.

8. The multi-metallic organometallic complex of claim 1 , wherein M 1 , M 2 , and M 3 are independently selected from the group consisting of nickel, titanium, zirconium, yttrium, hafnium, cobalt, iron, palladium, aluminum, zinc, indium, gallium and a lanthanide metal.

9. A method for preparing a polyolefin, the method comprising contacting an olefin monomer with the multi-metallic organometallic complex of claim 1 for a time and under condition to allow polymerization to the olefin monomers.

10. The method of claim 9 , wherein the olefin monomer is polar monomer.

11. The method according to claim 9 , further comprising contacting the olefin monomer and the multi-metallic organometallic complex with a suitable activator or a phosphine scavenger.

12. The method according to claim 9 wherein the polyolefin is isotactic.

13. A polyolefin, obtainable by the method according to claim 9 .

14. A method for preparing polyolefin copolymers, the method comprising contacting two or more olefin monomers with the multi-metallic organometallic complex of claim 1 .

15. A method for preparing a polyolefin block copolymer, the method comprising sequentially contacting two or more olefin monomers, each of the two or more olefin monomers being structurally different from another, with the multi-

Assignees

• Radlauer Madalyn
• Wiensch Joshua D
• Buckley Aya K
• Agapie Theodor
• California Inst Of Techn

Inventors

• Radlauer Madalyn
• Wiensch Joshua D
• Buckley Aya K
• Agapie Theodor

Classifications

• C07F7/003

  without C-Metal linkages · CPC title

• C08F4/60003

  the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond · CPC title

• C07F15/04

  Nickel compounds · CPC title

• C08F4/619

  Component covered by group C08F4/60 containing a transition metal-carbon bond {(C08F4/60003 - C08F4/60196 take precedence)} · CPC title

• C08F110/02

  Ethene · CPC title