CATALYSTS FOR EPOXIDE CARBONYLATION

• US 20170080409A1
• Filed: 03/13/2015
• Published: 03/23/2017
• Est. Priority Date: 03/14/2014
• Status: Abandoned Application

• Current Assignee: Novomer, Inc (Danimer Scientific, Inc.)
• Original Assignee: Novomer, Inc (Danimer Scientific, Inc.)
• Inventors: Farmer, Jay J., Allen, Scott D.
• Application Number:
  US15/126,266
• Publication Number:
  US 20170080409A1
• Time in Patent Office: Days
• CPC Class Codes: B01J 2231/14 Other (co) polymerisation, e.g. of lactides, epoxides "ROMP", i.e. ring-opening metathesis polymerisation B01J2231/54
• CPC Class Codes: B01J 2231/34 Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
• CPC Class Codes: B01J 2531/0205 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
• 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 2531/31 Aluminium
• CPC Class Codes: B01J 2531/62 Chromium
• CPC Class Codes: B01J 2531/845 Cobalt
• CPC Class Codes: B01J 31/1805 the ligands containing nitrogen
• CPC Class Codes: B01J 31/1815 with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
• CPC Class Codes: B01J 31/20 Carbonyls
• CPC Class Codes: B01J 31/2217 At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
• CPC Class Codes: C07F 5/069 without C-aluminium linkages

Abstract

The present invention encompasses catalysts for the carbonylation of heterocycles such as ethylene oxide, as well as methods for their use. The catalysts feature Lewis acidic metal complexes having one or more tethered metal-coordinating groups in combination with at least one metal carbonyl species. In preferred embodiments, the inventive catalysts have improved stability when subjected to product separation conditions in continuous ethylene oxide carbonylation processes.

Claims

1. A metal complex for the carbonylation of heterocycles comprising the combination of:

i) one or more tethered metal-coordinating moieties, where each metal-coordinating moiety comprises a linker and 1 to 4 metal-coordinating groups;

ii) one or more ligands to which the one or more metal-coordinating moieties are covalently tethered, wherein the one or more ligands are coordinated to one or two metal atoms; and

iii) at least one metal carbonyl species associated with a metal-coordinating moiety present on the metal complex.

2. The metal complex of claim 1, wherein the one or more ligands to which at least one metal-coordinating moiety is covalently tethered is selected from the group consisting of porphryin ligands and salen ligands.

3. The metal complex of claim 2, wherein metal complex comprises a salen or porphyrin complex of a metal selected from the group consisting of:

Zn(II), Cu(II), Mn(II), Co(II), Ru(II), Fe(II), Co(II), Rh(II), Ni(II), Pd(II), Mg(II), Al(III), Cr(III), Fe(III), Co(III), Ti(III), In(III), Ga(III), Mn(III).

4. The metal complex of claim 2, wherein the metal complex comprises a salen or porphyrin complex of aluminum.

5. The metal complex of claim 2, wherein the metal complex comprises a salen or porphyrin complex of chromium.

6. The metal complex of claim 1, wherein a metal-coordinating moiety comprises one or more functional groups containing an atom selected from the group consisting of:

phosphorous, nitrogen atom, and boron.

7. A method for the carbonylation of heterocycles comprising contacting a heterocycle and carbon monoxide in the presence of a metal complex of claim 1.

8. The method of claim 7, wherein the heterocycle is an epoxide, aziridine, thiirane, oxetane, lactone, or lactam.

9. The method of claim 8, wherein the heterocycle is ethylene oxide.