Catalysts and methods for polymer synthesis

Patent metadata

Field	Value
Publication number	US-9580547-B2
Application number	US-201615171755-A
Country	US
Kind code	B2
Filing date	Jun 2, 2016
Priority date	Nov 4, 2011
Publication date	Feb 28, 2017
Grant date	Feb 28, 2017

Abstract

The present invention provides unimolecular metal complexes having increased activity in the copolymerization of carbon dioxide and epoxides. Also provided are methods of using such metal complexes in the synthesis of polymers. According to one aspect, the present invention provides metal complexes comprising an activating species with co-catalytic activity tethered to a multidentate ligand that is coordinated to the active metal center of the complex.

First claim

What is claimed is:

1. A method for the synthesis of aliphatic polycarbonates comprising the step of contacting an epoxide and carbon dioxide with a metal complex comprising a metal atom coordinated with a salen ligand, the salen ligand comprising two halves, each half coordinated to the metal atom via an imine and an oxygen atom, wherein the metal complex is characterized in that one of the two halves of the salen ligand has two or more cationic activating functional groups tethered to it and the other half has no tethered cationic activating functional groups, wherein the metal complex is of formula IVa:

wherein,
M is a metal atom;
X is a nucleophile capable of ring opening an epoxide;
k is an integer from 0-2 inclusive;
R′ represents one or more substituents optionally present on the phenyl rings and each R′ is independently selected from the group consisting of: halogen, —NO 2 , —CN, —SR y , —S(O)R y , —S(O) 2 R y , —NR y C(O)R y , —OC(O)R y , —CO 2 R y , —NCO, —N 3 , —OR 7 , —OC(O)N(R y ) 2 , —N(R y ) 2 , —NR y C(O)R y , —NR y C(O)OR y ; or an optionally substituted radical selected from the group consisting of C 1-20 aliphatic; C 1-20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, where two or more adjacent R′ groups can be taken together to form an optionally substituted saturated, partially unsaturated, or aromatic 5- to 12-membered ring containing 0 to 4 heteroatoms;
R y is —H, or an optionally substituted radical selected from the group consisting of C 1-6 aliphatic, 3- to 7-membered heterocyclic, phenyl, and 8- to 10-membered aryl;
R 4a , R 6a , and R 7a are each independently a (Z) m group, hydrogen, halogen, —OR, —NR 2 , —SR, —CN, —NO 2 , —SO 2 R, —SOR, —SO 2 NR 2 ; —CNO, —NRSO 2 R, —NCO, —N 3 , —SiR 3 ; or an optionally substituted radical selected from the group consisting of C 1-20 aliphatic; C 1-20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein R at each occurrence is independently hydrogen, an optionally substituted radical selected the group consisting of acyl; C 1-6 aliphatic; C 1-6 heteroaliphatic; carbamoyl; arylalkyl; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; an oxygen protecting group; and a nitrogen protecting group, where two R groups on the same nitrogen atom can optionally be taken together to form an optionally substituted 3- to 7-membered ring;
wherein R 6a and R 7a can be taken together with intervening atoms to form one or more optionally substituted rings;
R 7 is hydrogen, a hydroxyl protecting group, or an optionally substituted radical selected from the group consisting of C 1-20 acyl; C 1-20 aliphatic; C 1-20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
represents an optionally substituted moiety linking the two nitrogen atoms of the diamine portion of the salen ligand, where is selected from the group consisting of phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an optionally substituted C 2-20 aliphatic group, wherein one or more methylene units are optionally and independently replaced by —NR y —, —N(R y )C(O)—, —C(O)N(R y )—, —OC(O)N(R y )—, —N(R y )C(O)O—, —OC(O)O—, —O—, —C(O)—, —OC(O)—, —C(O)O—, —S—, —SO—, —SO 2 —, —C(═S)—, —C(═NR y )—, —C(═NOR y )— or —N═N—; and
(Z) m represents one or more activating moieties, where “ ” is a covalent linker containing one or more atoms selected from the group consisting of C, O, N, S, and Si; Z is a cationic functional group and each m is independently an integer from 1 to 4 indicating the number of individual cationic functional groups present in each activating moiety;
wherein a total of at least two cationic functional groups (Z) are present,
wherein each cationic activating functional group (Z) is independently a phosphorus-containing functional group or

where X − is any anion; and
R 11 , R 12 , and R 13 are each independently C 1 -C 20 alkyl; C 1 -C 20 alkyl having one or more functional moieties selected from the group consisting of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; C 2 -C 20 alkenyl; C 2 -C 20 alkenyl having one or more functional moieties selected from the group consisting of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; C 7 -C 20 alkylaryl; C 7 -C 20 alkylaryl having one or more functional m

Assignees

• Novomer Inc

Inventors

• Allen Scott D
• Job Gabriel
• Farmer Jay J

Classifications

• C08G64/34 Primary

  and cyclic ethers · CPC title

• B01J31/2217

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

• C08G64/02

  Aliphatic polycarbonates · CPC title

• B01J2540/42

  Quaternary ammonium groups · CPC title

• C07F15/065

  without a metal-carbon linkage · CPC title