Catalysts and methods for polymer synthesis

• US 9,505,878 B2
• Filed: 02/06/2015
• Issued: 11/29/2016
• Est. Priority Date: 08/22/2008
• Status: Active Grant

• Current Assignee: Saudi Aramco Technologies Company
• Original Assignee: Novomer, Inc (Danimer Scientific, Inc.)
• Inventors: Allen, Scott D., Cherian, Anna E., Simoneau, Chris A., Farmer, Jay J., Coates, Geoffrey W., Gridnev, Alexei, LaPointe, Robert E.
• Primary Examiner(s): Troung, Duc
• Application Number:
  US14/615,902
• Publication Number:
  US 20150252145A1
• Time in Patent Office: 662 Days
• Field of Search: 528/371, 556/33, 548/106, 546/6, 544/64, 544/225
• US Class Current: 1/1
• 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 having the structure:

2. The metal complex of claim 1, wherein M is selected from the group consisting of Cr, Co, and Al.

3. The metal complex of claim 1, wherein M is Cr.

4. The metal complex of claim 1, wherein M is Co.

5. The metal complex of claim 1, wherein the metal complex is:

6. The metal complex of claim 1, wherein the moiety contains 1-30 atoms including at least one carbon atom, and optionally one or more atoms selected from the group consisting of N, O, S, Si, B, and P.

7. The metal complex of claim 1, wherein the moiety is a C_2-30 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)—

, —

O—

, —

C(O)—

, —

OC(O)—

, —

C(O)O—

, —

S—

, —

Si(R^y)₂—

, —

SO—

, —

SO₂—

, —

C(═

S)—

, —

C(═

NR^y)—

, or —

N═

N—

, where each occurrence of R^y is independently —

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.

8. The metal complex of claim 1, wherein the moiety is selected from the group consisting of:

9. The metal complex of claim 1, wherein each Z group is independently selected from the group consisting of:

10. The metal complex of claim 1, wherein at least one Z group is selected from the group consisting of amidine, guanidine, amidinium, and guanidinium.

11. The metal complex of claim 9, wherein at least one Z group is selected from the group consisting of

12. The metal complex of claim 11, wherein at least one Z group is selected from the group consisting of:

13. The metal complex of claim 9, wherein at least one Z group is selected from the group consisting of:

14. The metal complex of claim 13, wherein at least one Z group is selected from the group consisting of:

15. The metal complex of claim 9, wherein at least one Z group is selected from the group consisting of:

16. The metal complex of claim 9, wherein at least one Z group is

17. The metal complex of claim 1, wherein at least one Z group is selected from the group consisting of:

18. The metal complex of claim 9, wherein at least one Z group is selected from the group consisting of:

19. The metal complex of claim 1, wherein at least one Z group is selected from the group consisting of:

20. The metal complex of claim 1, wherein the compound is selected from the group consisting of:

21. The metal complex of claim 20, wherein M is selected from Cr, Co, or Al.

22. The metal complex of claim 20, wherein Xis 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.

23. The metal complex of claim 20, wherein wherein X is selected from the group consisting of chloride, acetate, trifluoroacetate, azide, pentafluorobenzoate, and a nitrophenolate.

24. The metal complex of claim 1 selected from the group consisting of:

25. The metal complex of claim 1 selected from

26. A method comprising the step of contacting an epoxide and carbon dioxide with a polymerization catalyst selected from the metal complex of claim 1.

27. A metal complex: