Iron complexes and methods for polymerization

Patent metadata

Field	Value
Publication number	US-9290591-B2
Application number	US-201213984292-A
Country	US
Kind code	B2
Filing date	Feb 8, 2012
Priority date	Feb 8, 2011
Publication date	Mar 22, 2016
Grant date	Mar 22, 2016

Abstract

Provided are methods of preparing polymers, such as polyisoprene, polybutadiene, polypiperylene, polycyclohexadiene, poly-β-farnesene, or poly-β-myrcene, using iron complexes. Also provided are novel iron complexes, pre-catalysts, intermediates, and ligands useful in the inventive polymerization system.

First claim

What is claimed is:

1. A method of preparing a polymer, the method comprising polymerizing one or more alkenes in the presence of an iron complex, wherein the iron complex comprises a ligand of the Formula (BI-a):

wherein:
m is 0 or 1, provided that when m is 0, X is selected from N—R 4 ; and when m is 1, X is selected from N or C—R 4 ;
each instance of R 1 , R 2 , R 3 , R 4 , and R 5 is independently selected from the group consisting of hydrogen, halogen, —CN, —NO 2 , —N 3 , —SO 2 H, —SO 3 H, —OH, —SH, —NH 2 , substituted hydroxyl, substituted thiol, monosubstituted amino, disubstituted amino, trisubstituted amino, sulfonyl, sulfinyl, carbonyl, silyl, phosphino, boronyl, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, and optionally substituted heteroaryl; or R 1 and R 2 , or R 2 and R 3 , or R 2 and R 4 , or R 3 and R 4 , are optionally joined to form a ring selected from the group consisting of optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, and optionally substituted heteroaryl ring;
R 7 is optionally substituted aryl or optionally substituted —CH 2 aryl;
R 8 and R 9 are each independently selected from the group consisting of hydrogen, halogen, —CN, —NO 2 , —N 3 , —SO 2 H, —SO 3 H, —OH, —SH, —NH 2 , substituted hydroxyl, substituted thiol, monosubstituted amino, disubstituted amino, trisubstituted amino, sulfonyl, sulfinyl, carbonyl, silyl, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, and optionally substituted heteroaryl,
and the one or more alkenes are independently an optionally substituted 1,3-diene of formula (i):

wherein:
each instance of R a , R b , R c , R d , R e , and R f is independently selected from the group consisting of hydrogen, silyl, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, and optionally substituted heteroaryl;
or R a and R f are joined to form an optionally substituted heterocyclyl or optionally substituted carbocyclyl ring.

2. The method according to claim 1 , wherein the ligand is of the Formula (BI-b):

wherein:
each instance of R 10a , R 11a , R 12a , R 13a , and R 14a is independently selected from the group consisting of hydrogen, halogen, —CN, —NO 2 , —N 3 , —SO 2 H, —SO 3 H, —OH, —SH, —NH 2 , substituted hydroxyl, substituted thiol, monosubstituted amino, disubstituted amino, trisubstituted amino, sulfonyl, sulfinyl, carbonyl, silyl, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, and optionally substituted heteroaryl.

3. A method of preparing polyisoprene, the method comprising polymerizing isoprene in the presence of an iron complex, wherein the iron complex comprises a ligand of Formula (BI-a):

wherein:
m is 0 or 1, provided that when m is 0, X is selected from N—R 4 ; and when m is 1, X is selected from N or C—R 4 ;
each instance of R 1 , R 2 , R 3 , R 4 , and R 5 is independently selected from the group consisting of hydrogen, halogen, —CN, —NO 2 , —N 3 , —SO 2 H, —SO 3 H, —OH, —SH, —NH 2 , substituted hydroxyl, substituted thiol, monosubstituted amino, disubstituted amino, trisubstituted amino, sulfonyl, sulfinyl, carbonyl, silyl, phosphino, boronyl, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, and optionally substituted heteroaryl; or R 1 and R 2 , R 2 and R 3 , R 2 and R 4 , or R 3 and R 4 are optionally joined to form a ring selected from the group consisting of optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, and optionally substituted heteroaryl ring;
R 7 is optionally substituted aryl or optionally substituted —CH 2 aryl; and
R 8 and R 9 are each independently selected from the group consisting of hydrogen, halogen, —CN, —NO 2 , —N 3 , —SO 2 H, —SO 3 H, —OH, —SH, —NH 2 , substituted hydroxyl, substituted thiol, monosubstituted amino, disubstituted amino, trisubstituted amino, sulfonyl, sulfinyl, carbonyl, silyl, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, and optionally substituted heteroaryl.

4. The method according to claim 3 , wherein the ligand is of the Formula (BI-b):

wherein:
each instance of R 10a , R 11a , R 12a , R 13a , and R 14a is independently selected from the group consisting of hydrogen, halogen, —CN, —NO 2 , —N 3 , —SO 2 H, —SO 3 H, —OH, —SH, —NH 2 , substituted hydroxyl, substituted thiol, monosubstituted amino, disubstituted amino, trisubstituted amino, sulfonyl, sulfinyl, carbonyl, silyl, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, and optionally substituted heteroaryl.

5. The method according to claim 4 , wherein the ligand is of the Formula (BI-c):

wherein:
each instance of R 10b , R 11b , R 12b , R 13b , and R 14b is independently selected from the group consisting of hydrogen, halogen, —CN, —NO 2 , —N 3 , —SO 2 H, —SO 3 H, —OH, —SH, —NH 2 , substituted hydroxyl, substituted thiol, monosubstituted amino, disubstituted amino, trisubstituted amino, sulfonyl, sulfinyl, carbonyl, silyl, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, and optionally substituted heteroaryl; and
R 9 is hydrogen or optionally substituted alkyl.

6. The method according to claim 3 , wherein the ligand is selected from the group consisting of:

Assignees

• Ritter Tobias
• Raynaud Jean B
• Wu Jessica Yung
• Harvard College

Inventors

• Ritter Tobias
• Raynaud Jean B
• Wu Jessica Yung

Classifications

• C08F36/08 Primary

  Isoprene · CPC title

• C08F2410/03

  Multinuclear procatalyst, i.e. containing two or more metals, being different or not · CPC title

• C08F4/80

  selected from iron group metals or platinum group metals · CPC title

• B01J31/1815

  with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine · CPC title

• C07F15/02

  Iron compounds · CPC title