Catalysts and methods for epoxide-based polymerizations

Patent metadata

Field	Value
Publication number	US-11260379-B2
Application number	US-202016898377-A
Country	US
Kind code	B2
Filing date	Jun 10, 2020
Priority date	Jun 10, 2019
Publication date	Mar 1, 2022
Grant date	Mar 1, 2022

Abstract

Provided are catalysts, methods of making catalysts, methods of using catalysts, and copolymers made utilizing the catalysts. The catalyst has a metal salen complex group, a bridging group, and one or more co-catalyst groups. The metal salen complex group is attached to the bridging group and the bridging group is attached to the co-catalyst group. The copolymers made utilizing the catalysts are polyesters or polycarbonates.

First claim

The invention claimed is:

1. A catalyst having the following structure:

wherein
M is chosen from Al, Co, Cr, Fe, Zn, Mn, Ti, Ni, Ga, Sm, Y, and V;

is chosen from

R 1 and R 2 are independently at each occurrence chosen from hydrogen, linear alkyl groups, branched alkyl groups, cycloaliphatic groups, polycycloaliphatic groups, unsaturated aliphatic groups, aryl groups, heterocyclic groups, heteroaliphatic groups, halogen-containing aliphatic groups, halogenated aliphatic groups, nitrile groups, and onium groups;
R 3 , R 4 , R 5 , and R 6 are independently at each occurrence chosen from hydrogen, linear alkyl groups, branched alkyl groups, cycloaliphatic groups, polycycloaliphatic groups, unsaturated aliphatic groups, and aryl groups;
X is an anion chosen from F, Cl, Br, I, N 3 , NO 3 , carboxylates, benzoates, alkoxides, phenoxides, enolates, thiolates, amides, sulfonamides, thiocyanates, CN, O(SO 2 )R, BPh 4 , SbF 6 , and ClO 4 ; and
Y is optional and is a ligand chosen from F, Cl, Br, I, N 3 , NO 3 , carboxylates, benzoates, alkoxides, phenoxides, enolates, thiolates, amides, sulfonamides, thiocyanates, CN, O(SO 2 )R, BPh 4 , SbF 6 , and ClO 4 .

2. The catalyst of claim 1 , wherein the catalyst is:

wherein Cy is a cyclohexyl group.

3. The catalyst of claim 2 , wherein the catalyst is:

wherein Cy is a cyclohexyl group.

4. The catalyst of claim 1 , wherein the catalyst is:

wherein Cy is a cyclohexyl group.

5. The catalyst of claim 1 , wherein the catalyst is:

wherein Cy is a cyclohexyl group.

6. A method of making a catalyst of claim 1 , comprising:
contacting a bridging group precursor, wherein the bridging group precursor is chosen from:

with one or more substituted or unsubstituted salicylaldehyde(s), wherein the substituted or unsubstituted salicylaldehyde(s) independently have the following structure:

wherein R 1 and R 2 are independently chosen from hydrogen, linear alkyl groups, branched alkyl groups, cycloaliphatic groups, polycycloaliphatic groups, unsaturated aliphatic groups, aryl groups, heterocyclic groups, heteroaliphatic groups, halogen-containing aliphatic groups, halogenated aliphatic groups, nitrile groups, and onium groups, such that a first reaction product is formed;
contacting the first reaction product with an alkyl halide-functionalized co-catalyst, wherein the alkyl halide-functionalized co-catalyst has the following structure:

wherein R 3 , R 4 , R 5 , and R 6 are independently chosen from hydrogen, linear alkyl groups, branched alkyl groups, cycloaliphatic groups, polycycloaliphatic groups, unsaturated aliphatic groups, and aryl groups and X is an anion chosen from F, CI, Br, I, N 3 , NO 3 carboxylates, benzoates, alkoxides, phenoxides, enolates, thiolates, amides, sulfonamides, thiocyanates, CN, O(SO 2 )R, BPh 4 , SbF 5 and ClO 4 and Z is a halogen, that may have one or more substituent(s) such that a second reaction product is formed;
contacting the second reaction product with a Lewis acid such that the catalyst is formed;
optionally, oxidizing the catalyst; and
optionally, isolating the catalyst.

7. The method of claim 6 , wherein the Lewis acid comprises an oxidized metal (M) and one or more ligand(s), wherein the ligand(s) is/are chosen from alkyl groups, alkoxides, phenoxides, azide, nitrate, acetate, carboxylate, halides, and combinations thereof, and, optionally, the Lewis acid is a hydrate.

8. The method of claim 7 , wherein the Lewis acid is chosen from Et 2 AlCl, Me 2 Zn, CrCl 2 , Mn(OAc) 3 .2H 2 O, FeCl 3 .6H 2 O, and Co(OAc) 2 .4H 2 O.

9. The method of claim 6 , wherein the catalyst is:

wherein Cy is a cyclohexyl group.

10. A method of making an aliphatic polyester or an aliphatic polycarbonate, comprising
contacting an epoxide with i) a cyclic anhydride or CO 2 and ii) a catalyst of claim 1 ,

wherein the aliphatic polyester or the aliphatic polycarbonate is formed.

11. The method of claim 10 , wherein the ratio of catalyst to cyclic anhydride to epoxide or catalyst to CO 2 to epoxide is 1:≥100: >100 and there is more epoxide than cyclic anhydride.

12. The method of claim 10 , wherein the epoxide is chosen from:

wherein R is a substituted or unsubstituted aliphatic group.

13. The method of claim 10 , wherein the cyclic anhydride is chosen from:
substituted or unsubstituted cyclic anhydride Diels Alder adducts, substituted or unsubstituted

substituted or unsubstituted

substituted or unsubstituted

substituted or unsubstituted

substituted or unsubstituted

substituted or unsubstituted

substituted or unsubstituted

substituted or unsubstituted

and substituted or unsubstituted

14. The method of claim 10 , further comprising heating the mixture.

15. The method of claim 10 , further comprising contacting the epoxide with one or more protic chain transfer agent(s) prior to contacting the epoxide with the cyclic anhydride.

16. The method of claim 10 , wherein the catalyst is:

wherein Cy is a cyclohexyl group.

Assignees

• Univ Cornell

Inventors

• Coates Geoffrey W
• Abel Brooks
• Lidston Claire

Classifications

• B01J2531/0252

  Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde · CPC title

• C08G64/02

  Aliphatic polycarbonates · CPC title

• B01J2531/31

  Aluminium · CPC title

• B01J31/143 Primary

  of aluminium · CPC title

• C08G63/84

  Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds thereof {(C08G63/823 takes precedence)} · CPC title