Copolymerization of ethylene oxide and carbon dioxide

Patent metadata

Field	Value
Publication number	US-10214614-B2
Application number	US-201514627733-A
Country	US
Kind code	B2
Filing date	Feb 20, 2015
Priority date	May 9, 2008
Publication date	Feb 26, 2019
Grant date	Feb 26, 2019

Abstract

The present disclosure is directed, in part, to methods of synthesizing a poly(ethylene carbonate) polymer from the reaction of ethylene oxide (EO) and carbon dioxide (CO 2 ) in the presence of a metal complex. The present disclosure also provides novel metal complexes. In one aspect, the metal complex is of the formula (I), wherein R 1 , R 2 , R 3 , M, X and Ring A are as defined herein.

First claim

We claim:

1. A method of synthesizing a poly(ethylene carbonate) polymer,
wherein the polymer is made up of Y, and optionally Z, the percentage of Y is greater than the percentage of Z, and the polymer has greater than 95% of Y,

the method comprising reacting ethylene oxide and carbon dioxide in the presence of a metal complex, wherein the metal complex is of the formula:

wherein:
M is a metal selected from zinc, cobalt, chromium, aluminum, titanium, ruthenium or manganese;
X is absent or is a nucleophilic ligand;
each instance of R 3 is, independently, selected from hydrogen, halogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, and optionally substituted heteroaryl;
R 7 and R 9 are, independently, selected from hydrogen, halogen, —OR c , —OC(═O)R c , —OC(═O)OR c , —OC(═O)N(R d ) 2 , —OSO 2 R d , —C(═O)OR c , —C(═O)N(R d ) 2 , —CN, —CNO, —NCO, —N 3 , —NO 2 , —N(R d ) 2 , —N(R d )C(═O)OR c , —N(R d )C(═O)R c , —N(R d )SO 2 R d , —SO 2 R d , —SOR d , —SO 2 N(R d ) 2 , optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, optionally substituted heteroaryl, wherein each instance of R c is, independently, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, optionally substituted heteroaryl, and each instance of R d is, independently, hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, optionally substituted heteroaryl;
wherein the A value of at least one of R 7 and R 9 is greater than the A-value of tert-butyl; and
Ring A forms an optionally substituted 5- to 6-membered ring.

2. The method according to claim 1 , wherein the metal complex is of the formula:

3. The method according to claim 1 , wherein the metal complex is of the formula:

4. The method according to claim 1 , wherein R 7 is an optionally substituted C 1-10 aliphatic group.

5. The method according to claim 1 , wherein R 7 is an optionally substituted C 1-10 alkyl group.

6. The method according to claim 1 , wherein R 7 is selected from methyl, trichloromethyl, trifluoromethyl, ethyl, n-propyl, isopropyl, t-butyl, sec-butyl, iso-butyl, n-pentyl, neopentyl, amyl, trityl, adamantyl, thexyl, benzyl and cumyl.

7. The method according to claim 1 , wherein R 9 is an optionally substituted C 1-10 aliphatic group.

8. The method according to claim 1 , wherein R 9 is an optionally substituted C 1-10 alkyl group.

9. The method according to claim 1 , wherein R 9 is selected from methyl, trichloromethyl, trifluoromethyl, ethyl, n-propyl, isopropyl, t-butyl, sec-butyl, iso-butyl, n-pentyl, neopentyl, amyl, trityl, adamantyl, thexyl, benzyl and cumyl.

10. The method according to claim 1 , wherein the A-value of R 9 is between about 0 to about 2.5 kcal/mol.

11. The method according to claim 1 , wherein the metal complex is selected from any of the following formulae:

12. The method according to claim 1 , wherein M is cobalt.

13. The method according to claim 1 , wherein X is absent or is selected from the group consisting of: —OR x , —SR x , —O(C═O)R x , —O(C═O)OR x , —O(C═O)N(R x ) 2 , —N(R x )(C═O)R x , —NC, —CN, halo, —N 3 , —O(SO 2 )R x and —OPR x , wherein each R x is, independently, selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl and optionally substituted heteroaryl.

14. The method according to claim 1 , wherein X is —O(C═O)C 6 F 5 , —O(C═O)C 6 H 5 , —O(C═O)CF 3 , —O(C═O)CH 3 , —NC, —CN, —N 3 , —Cl, or —Br.

15. The method according to claim 14 , wherein X is —O(C═O)C 6 F 5 .

16. The method according to claim 1 , wherein the reaction further comprises a co-catalyst, wherein the co-catalyst is a salt.

17. The method according to claim 16 , wherein the salt is an ammonium, phosphonium, or arsonium salt.

18. The method according to claim 17 , wherein the ammonium salt is (n-Bu) 4 NCl, (n-Bu) 4 NBr, (n-Bu) 4 NN 3 , [PPN]Cl, [PPN]Br, or [PPN]N 3 .

19. The method according to claim 1 , wherein the polymer has greater than about 99% of Y.

20. The method according to claim 19 , wherein the polymer is 100% of Y and 0% of Z.

21. The method according to claim 1 , wherein the polymer is of the formula:

P is an integer of between about 10,000 and about 15,000, inclusive; and
F and G are, independently, suitable terminating groups.

22. A method of synthesizing a poly(ethylene carbonate) polymer, comprising a step of reacting ethylene oxide with carbon dioxide in the presence of a cobalt complex,
wherein the cobalt complex is any one of the formulae:

wherein X is absent or is a nucleophilic ligand; and
wherein the polymer has greater than 95% carbonate linkages.

23. A metal complex of the formula:

wherein:
M is a metal selected from zinc, cobalt, chromium, aluminum, titanium, ruthenium or manganese;
X is absent or is a nucleophilic ligand;
R 7 and R 9 are, independently, selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, optionally substituted heteroaryl;
wherein the A value of at least one of R 7 and R 9 is greater than the A-value of tert-butyl; and
R 4A , R 4B , R 5A , R 5B , and R 6A , R 6B are, independently, selected from hydrogen, halogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, optionally substituted heteroaryl, and/or, R 4A and R 4B , and/or R 5A and R 5B , and/or and R 6A and R 6B are optionally joined to form an oxo (═O) group, an oxime (═NOR a ) group, an imine (═NN(R a ) 2 ) group, an alkenyl (═C(R b ) 2 ) group, and/or a 3- to 6-membered spirocyclic ring, wherein each instance of R a and R b is, independently, hydrogen or optionally substituted aliphatic, wherein optionally two R a groups or two R b groups are joined to form a 3- to 6-membered ring.

24. The method of claim 1 , wherein R 7 and R 9 are the same.

25. The method of claim 1 , wherein R 7 and R 9 are different.

Assignees

• Univ Cornell

Inventors

• Coates Geoffrey W
• Allen Scott
• Ando Tsuyoshi

Classifications

• C08G64/34 Primary

  and cyclic ethers · CPC title

• C08G64/183

  containing polyether sequences · CPC title

• C08G64/0208

  saturated · CPC title

• C07F15/065

  without a metal-carbon linkage · CPC title