# US 10,308,762 B2 · Bimetallic catalytic complexes for the polymerisation of carbon dioxide and an epoxide

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- Number: US 10,308,762 B2
- Document ID: US10308762B2
- Status: Granted
- Kind: B2
- Application number: 15/482,448
- Filed: 2017-04-07
- Published: 2017-08-31
- Granted: 2019-06-04
- Earliest claimed: 2014-10-28
- Assignees: Imperial Innovations Limited
- Applicants: Imperial Innovations Limited
- Inventors: Charlotte Katherine Williams; Michael Kember; Paul Knight
- Web page: https://patentgrep.com/patent/US10308762B2

## CPC

- C08G 64/34: and cyclic ethers
- B01J 31/1835: {comprising aliphatic or saturated rings}
- B01J 31/2239: {Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands}
- B01J 31/2243: {At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand}
- B01J 31/226: {Sulfur, e.g. thiocarbamates}
- C07C 217/58: with amino groups and the six-membered aromatic ring, or the condensed ring system containing that ring, bound to the same carbon atom of the carbon chain
- B01J 31/04: containing carboxylic acids or their salts {(B01J31/0277 - B01J31/0298 take precedence; multi-metal carboxylate complexes like Pd (II) acetate, i.e. Pd3 (OAc) 6 or Cr(II)acetate, i.e. Cr2(OAc)4 B01J31/2226)}
- B01J 2531/0216: Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
- B01J 2531/0241: Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J 2531/22: Magnesium
- B01J 2531/26: Zinc
- B01J 2531/62: Chromium
- B01J 2531/72: Manganese
- B01J 2531/842: Iron
- B01J 2531/845: Cobalt
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

The present invention provides a novel catalyst of formula (I): wherein M is selected from Zn(H), Co(II), Mn(II), Mg(II), Fe(II), Cr(III)—X or Fe(III)—X, and the use thereof in polymerizing carbon dioxide and an epoxide.

## Claims

### Claim 1

A dimeric catalyst wherein said dimeric catalyst comprises two monomeric subunits, wherein each monomeric subunit is a catalyst of formula (I):
wherein each R1 and R2 are independently hydrogen, alkyl, haloalkyl, aryl, halide, amine, a nitro group, an ether group, a silyl ether group, a nitrile group or an acetylide group;
each R3 is independently alkylene, arylene or cycloalkylene;
each R4 is independently H, alkyl, aryl or alkylaryl;
each E1 is C, each E2 is independently O, S or NH;
or each E1 is N and each E2 is O;
X is OCOCH3, OCOCF3, OSO2C7H7, OSO(CH3)2 or halide;
M is Zn(II), Cr(II), Co(II), Mn(II), Mg (II), Fe(II), Cr (III)—X, Co (III)—X, Mn (III)—X or Fe(III)—X;
and wherein the two monomeric subunits are linked by a bridging ligand X.

### Claim 2 (depends on 1)

The dimeric catalyst as claimed in claim 1, wherein said catalyst has the structure:
wherein:
X is OCOCH3, OCOCF3, OSO2C7H7, OSO(CH3)2, or halide.

### Claim 3 (depends on 1)

The dimeric catalyst as claimed in claim 1, wherein said catalyst has the structure:

### Claim 4 (depends on 1)

The dimeric catalyst as claimed in claim 1, wherein each R1 and R2 are independently selected from hydrogen, tBu, Me, CF3, phenyl, F, Cl, Br, I, NMe2, NEt2, NO2, OMe, OSiEt3, CNMe, CN, or CCPh.

### Claim 5 (depends on 1)

The dimeric catalyst as claimed in claim 1, wherein each R1 and R2 are independently selected from hydrogen, tBu, Me, F, Cl, Br, I, or OMe.

### Claim 6 (depends on 1)

The dimeric catalyst as claimed in claim 1, wherein R3 is ethylene, 2,2-dimethylpropylene, propylene, butylene, phenylene, cyclohexylene, or biphenylene.

### Claim 7 (depends on 1)

The dimeric catalyst as claimed in claim 1, wherein R3 is 2,2-dimethylpropylene or propylene.

### Claim 8 (depends on 1)

The dimeric catalyst as claimed in claim 1, wherein R4 is H, Me, Et, Bn, iPr, nBu, tBu, or Ph.

### Claim 9 (depends on 1)

The dimeric catalyst as claimed in claim 1, wherein R4 is H.

### Claim 10 (depends on 1)

The dimeric catalyst as claimed in claim 1, wherein X is OCOCH3, OCOCF3, OSO2C7H7, OSO(CH3)2, Cl, Br, or I.

### Claim 11 (depends on 1)

The dimeric catalyst as claimed in claim 1, wherein X is OCOCH3.

### Claim 12 (depends on 1)

The dimeric catalyst as claimed in claim 1, wherein each E1 is C, and each E2 is O.

### Claim 13 (depends on 1)

The dimeric catalyst as claimed in claim 1, wherein M is Zn(II), Cr(II), Co(II), Mg (II), Fe(II), Cr (III)—X, Co (III)—X, or Fe(III)—X.

### Claim 14 (depends on 1)

The dimeric catalyst as claimed in claim 1, wherein said dimeric catalyst comprises a bound water molecule.

### Claim 15 (depends on 1)

The dimeric catalyst of claim 1, wherein the monomeric subunits forming the dimeric catalyst have the same structure.

### Claim 16 (depends on 1)

A mixture comprising the dimeric catalyst of claim 1, wherein the monomeric subunits forming the dimeric catalyst have the same structure.

### Claim 17 (depends on 1)

A process for the reaction of carbon dioxide with an epoxide in the presence of a catalyst as claimed in claim 1.

### Claim 18 (depends on 17)

The process as claimed in claim 17, wherein the epoxide is selected from cyclohexene oxide, an alkylene oxide, or a substituted oxirane.

### Claim 19 (depends on 17)

The process as claimed in claim 17, wherein said process is carried out at 1 atmosphere.

### Claim 20 (depends on 17)

A product of the process of claim 17.

### Claim 21 (depends on 1)

A process for the production of a dimeric catalyst as claimed in claim 1, said process comprising reaction of a compound of formula (III)
with a metal complex comprising the groups M and X in the presence of water, wherein the groups X, R1, R2, R3, R4, M, E1 and E2 are as defined in claim 1.

### Claim 22 (depends on 21)

The process as claimed in claim 21, wherein said reaction occurs in the presence of base.