Catalysts and methods for polymer synthesis

• US 9,951,096 B2
• Filed: 08/30/2016
• Issued: 04/24/2018
• Est. Priority Date: 08/22/2008
• Status: Active Grant

• Current Assignee: Saudi Aramco Technologies Company
• Original Assignee: Saudi Aramco Technologies Company
• Inventors: Allen, Scott D., Cherian, Anna E., Simoneau, Chris A., Farmer, Jay J., Coates, Geoffrey W., Gridnev, Alexei, LaPointe, Robert E.
• Primary Examiner(s): Truong, Duc
• Application Number:
  US15/251,668
• Publication Number:
  US 20170183369A1
• Time in Patent Office: 602 Days
• Field of Search: 528371, 556 33, 548106, 546 6, 544 64, 544225
• CPC Class Codes: B01J 2531/0238 Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
• CPC Class Codes: B01J 2531/025 Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
• CPC Class Codes: B01J 2531/0252 Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
• CPC Class Codes: B01J 2531/0294 "Non-innocent" or "non-spectator" ligands, i.e. ligands described as, or evidently, taking part in the catalytic reaction beyond merely stabilizing the central metal as spectator or ancilliary ligands, e.g. by electron transfer to or from the central metal or by intra-/intermolecular chemical reactions, e.g. disulfide coupling, H-abstraction
• CPC Class Codes: B01J 2531/31 Aluminium
• CPC Class Codes: B01J 2531/62 Chromium
• CPC Class Codes: B01J 2531/845 Cobalt
• CPC Class Codes: B01J 31/0239 Quaternary ammonium compounds
• CPC Class Codes: B01J 31/0259 comprising phosphorous acid (-ester) groups ((RO)P(OR')2) or the isomeric phosphonic acid (-ester) groups (R(R'O)2P=O), i.e. R= C, R'= C, H
• CPC Class Codes: B01J 31/0265 Phosphazenes, oligomers thereof or the corresponding phosphazenium salts polyphosphazenes per se C07F9/067
• CPC Class Codes: B01J 31/182 comprising aliphatic or saturated rings
• CPC Class Codes: B01J 31/183 with more than one complexing nitrogen atom, e.g. phenanthroline
• CPC Class Codes: B01J 31/1835 comprising aliphatic or saturated rings
• CPC Class Codes: B01J 31/2243 At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
• CPC Class Codes: C07C 251/24 having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings
• CPC Class Codes: C07C 2601/14 The ring being saturated
• CPC Class Codes: C07C 279/12 being further substituted by nitrogen atoms not being part of nitro or nitroso groups
• CPC Class Codes: C07D 213/53 Nitrogen atoms
• CPC Class Codes: C07D 487/04 Ortho-condensed systems
• CPC Class Codes: C07D 487/22 in which the condensed system contains four or more hetero rings
• CPC Class Codes: C07F 15/065 : without a metal-carbon linkage
• CPC Class Codes: C07F 19/005 : without metal-C linkages
• CPC Class Codes: C07F 9/5355 : Phosphoranes containing the structure P=N-
• CPC Class Codes: C07F 9/6561 : containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings
• CPC Class Codes: C08F 4/80 : selected from iron group metals or platinum group metals
• CPC Class Codes: C08G 64/34 : and cyclic ethers

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.

Claims

1. A metal complex of the formula:

2. The metal complex according to claim 1, wherein

3. The metal complex according to claim 1, wherein

4. The metal complex according to claim 3, wherein each R^4a, R^4a′

, R^5a, R^5a′

, R^6a, R^6a′

, R^7a, and R^7a′

is independently selected from the group consisting of;

—

H, optionally substituted C_1-20 aliphatic, optionally substituted phenyl, and optionally substituted 8- to 10-membered aryl.

5. The metal complex according to claim 3, wherein at least one salicylaldehyde-derived portion of the polymerization catalyst is selected from the group consisting of:

6. The metal complex according to claim 3, wherein at least one salicylaldehyde-derived portion of the polymerization catalyst is selected from the group consisting of:

7. The metal complex according to claim 3, wherein each linker moiety

8. The metal complex according to claim 3, wherein each linker moiety

9. The metal complex according to claim 3, wherein each linker moiety

10. The metal complex according to claim 3, wherein each linker moiety

11. The metal complex according to claim 3, wherein each linker moiety

12. The metal complex of claim 3, wherein one or more Z group(s) is independently selected from the group consisting of:

13. The metal complex of claim 12, wherein one or more Z group(s) is independently selected from the group consisting of:

14. The metal complex of claim 13, wherein one or more Z group(s) is independently selected from the group consisting of:

15. The metal complex of claim 12, wherein one or more Z group(s) is independently selected from the group consisting of:

16. The metal complex of claim 15, wherein each R¹ and R² is methyl.

17. The metal complex of claim 12, wherein one or more Z group is independently selected from the group consisting of:

18. The metal complex according to claim 17, wherein one or more Z group is independently selected from the group consisting of:

19. The metal complex according to claim 3, wherein X is selected from the group consisting of:

chlorine, bromine, an optionally substituted C_1-12 carboxylate, azide, an optionally substituted phenoxide, a sulfonate salt, and a combination of any two or more of these.

20. The metal complex of claim 3, wherein one or more Z group(s) is independently selected from the group consisting of: