Process for production of acrylates from epoxides

• US 9,914,689 B2
• Filed: 10/11/2016
• Issued: 03/13/2018
• Est. Priority Date: 10/26/2011
• Status: Active Grant

• Current Assignee: Novomer, Inc (Danimer Scientific, Inc.)
• Original Assignee: Novomer, Inc (Danimer Scientific, Inc.)
• Inventors: Porcelli, Richard V., Farmer, Jay J., Lapointe, Robert E.
• Primary Examiner(s): BOYKIN, TERRESSA M
• Application Number:
  US15/291,011
• Publication Number:
  US 20170247309A1
• Time in Patent Office: 518 Days
• Field of Search: 528359
• CPC Class Codes: C07C 51/09 from carboxylic acid esters or lactones
• CPC Class Codes: C07C 51/12 on an oxygen-containing group in organic compounds, e.g. alcohols
• CPC Class Codes: C07C 57/04 Acrylic acid; Methacrylic acid
• CPC Class Codes: C07C 67/03 by reacting an ester group with a hydroxy group
• CPC Class Codes: C07C 67/36 by reaction with carbon monoxide or formates C07C67/02, C07C67/03, C07C67/10 take precedence
• CPC Class Codes: C07C 67/475 by splitting of carbon-to-carbon bonds and redistribution, e.g. disproportionation or migration of groups between different molecules
• CPC Class Codes: C07C 69/54 Acrylic acid esters; Methacrylic acid esters
• CPC Class Codes: C07D 301/08 in the gaseous phase
• CPC Class Codes: C07D 305/12 Beta-lactones
• CPC Class Codes: C08G 63/06 derived from hydroxycarboxylic acids
• CPC Class Codes: C08G 63/08 Lactones or lactides
• CPC Class Codes: C08G 63/81 using solvents C08G63/79 takes precedence
• CPC Class Codes: C08G 63/82 characterised by the catalyst used
• CPC Class Codes: C08G 63/823 for the preparation of polylactones or polylactides
• CPC Class Codes: Y02P 20/10 Process efficiency

Abstract

In one aspect, the present invention encompasses integrated processes for the conversion of epoxides to acrylic acid derivatives and polyesters. In certain embodiments, the methods of the present invention comprise the steps of: providing a feedstock stream comprising an epoxide and carbon monoxide; contacting the feedstock stream with a metal carbonyl in a first reaction zone to effect conversion of at least a portion of the provided epoxide to a beta lactone; directing the effluent from the first reaction zone to a second reaction zone where the beta lactone is subjected to conditions that convert it to a compound selected from the group consisting of: an alpha beta unsaturated acid, an alpha beta unsaturated ester, an alpha beta unsaturated amide, and an optionally substituted polypropiolactone polymer; and isolating a final product comprising the alpha-beta unsaturated carboxylic acid, the alpha-beta unsaturated ester, the alpha-beta unsaturated amide or the polypropiolactone.

Claims

1. A method for producing acrylic acid, comprising:

contacting ethylene oxide with carbon monoxide in the presence of a metal carbonyl compound supported on a solid support in a first reaction zone;

carbonylating at least a portion of the ethylene oxide in the first reaction zone to produce beta-propiolactone;

directing the beta-propiolactone to a second reaction zone; and

converting at least a portion of the beta-propiolactone in the second reaction zone to acrylic acid in the presence of a catalyst, wherein the conversion of the beta-propiolactone to the acrylic acid is performed in a continuous flow format.

2. The method of claim 1, further comprising isolating the acrylic acid from the second reaction zone.

3. The method of claim 1, where the catalyst in the second reaction zone comprises phosphoric acid, phosphorous pentoxide, aluminum oxide, iron oxide, titanium oxide, calcium hydroxide, magnesium hydroxide, or disodium phosphate, or any combinations thereof.

4. The method of claim 1, wherein the solid support comprises a polymeric support.

5. The method of claim 4, wherein the polymeric support comprises polystyrene, divinylbenzene, polyvinylpyridine, polymethylmethacrylate, a polyolefin, or polytetrafluoroethylene, or any combinations thereof.

6. The method of claim 1, wherein the solid support comprises an inorganic solid.

7. The method of claim 1, wherein the solid support comprises silica, glass, zirconia, diatomaceous earth, a metal oxide, a metal salt, a ceramic, a clay, a molecular sieve, kieselgur, or titanium dioxide, or any combinations thereof.

8. The method of claim 1, wherein the metal carbonyl compound has a formula [QM_y(CO)_w]^x, wherein:

Q is any ligand or more than one ligand and need not be present;

M is a metal atom;

y is an integer from 1 to 6 inclusive;

w is a number such as to provide the stable metal carbonyl; and

x is an integer from −

3 to +3 inclusive.

9. The method of claim 8, wherein M is Ti, Cr, Mn, Fe, Ru, Co, Rh, Ni, Pd, Cu, Zn, Al, Ga or In.

10. The method of claim 8, wherein M is Co.

11. The method of claim 1, wherein the metal carbonyl compound comprises Ti(CO)₇, V₂(CO)₁₂, Cr(CO)₆, Mo(CO)₆, W(CO)₆, Mn₂(CO)₁₀, Tc₂(CO)₁₀, Re₂(CO)₁₀, Fe(CO)₅, Ru(CO)₅, Os(CO)₅, Ru₃(CO)₁₂, Os₃(CO)₁₂, Fe₃(CO)₁₂, Fe₂(CO)₉, Co₄(CO)₁₂, Rh₄(CO)₁₂, Rh₆(CO)₁₆, Ir₄(CO)₁₂, Co₂(CO)₈, or Ni(CO)₄.

12. The method of claim 1, wherein the metal carbonyl compound comprises Co₂(CO)₈.

13. The method of claim 1, wherein the metal carbonyl compound comprises [Co(CO)₄]⁻

, [Ti(CO)₆]²⁻

, [V(CO)₆]⁻

, [Rh(CO)₄]⁻

, [Fe(CO)₄]²⁻

, [Ru(CO)₄]²⁻

, [Os(CO)₄]²⁻

, [Cr₂(CO)₁₀]²⁻

, [Fe₂(CO)₈]²⁻

, [Tc(CO)₅]⁻

, [Re(CO)₅]⁻

, or [Mn(CO)₅]⁻

.

14. The method of claim 1, wherein the metal carbonyl compound comprises [Co(CO)₄]⁻

.

15. A method for producing an acrylate ester, comprising:

contacting ethylene oxide with carbon monoxide in the presence of a metal carbonyl compound supported on a solid support in a first reaction zone;

carbonylating at least a portion of the ethylene oxide in the first reaction zone to produce beta-propiolactone;

directing the beta-propiolactone and a C_1-20 alcohol to a second reaction zone; and

converting at least a portion of the beta-propiolactone and the C_1-20 alcohol in the second reaction zone to an acrylate ester in the presence of a catalyst, wherein the conversion of the beta-propiolactone and C_1-20 alcohol to the acrylate ester is performed in a continuous flow format.

16. The method of claim 15, further comprising isolating the acrylate ester from the second reaction zone.

17. The method of claim 15, wherein the C_1-20 alcohol is methanol, ethanol, propanol, butanol, hexanol, 2-ethyl-hexanol, allyl alcohol, beta-ethoxy-ethyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, n-decyl alcohol, n-undecyl alcohol, cetyl alcohol, n-dodecyl alcohol, n-tetradecyl alcohol, diethylene glycol monoethyl ether, cyclohexanol, furfuryl alcohol, benzyl alcohol, or ethylene glycol, or any combinations thereof.

18. The method of claim 15, wherein the C_1-20 alcohol is a C_1-8 alcohol.

19. The method of claim 15, wherein the catalyst in the second reaction zone comprises a metal oxide, zeolite, silica, alumino-silicate, or activated carbon, or any combinations thereof.

20. The method of claim 15, wherein the solid support comprises a polymeric support.

21. The method of claim 20, wherein the polymeric support comprises polystyrene, divinylbenzene, polyvinylpyridine, polymethylmethacrylate, a polyolefin, or polytetrafluoroethylene, or any combinations thereof.

22. The method of claim 15, wherein the solid support comprises an inorganic solid.

23. The method of claim 15, wherein the solid support comprises silica, glass, zirconia, diatomaceous earth, a metal oxide, a metal salt, a ceramic, a clay, a molecular sieve, kieselgur, or titanium dioxide, or any combinations thereof.

24. The method of claim 15, wherein the metal carbonyl compound has a formula [QM_y(CO)_w]^x, wherein:

Q is any ligand or more than one ligand and need not be present;

M is a metal atom;

y is an integer from 1 to 6 inclusive;

w is a number such as to provide the stable metal carbonyl; and

x is an integer from −

3 to +3 inclusive.

25. The method of claim 24, wherein M is Ti, Cr, Mn, Fe, Ru, Co, Rh, Ni, Pd, Cu, Zn, Al, Ga or In.

26. The method of claim 24, wherein M is Co.

27. The method of claim 15, wherein the metal carbonyl compound comprises Ti(CO)₇, V₂(CO)₁₂, Cr(CO)₆, Mo(CO)₆, W(CO)₆, Mn₂(CO)₁₀, Tc₂(CO)₁₀, Re₂(CO)₁₀, Fe(CO)₅, Ru(CO)₅, Os(CO)₅, Ru₃(CO)₁₂, Os₃(CO)₁₂, Fe₃(CO)₁₂, Fe₂(CO)₉, Co₄(CO)₁₂, Rh₄(CO)₁₂, Rh₆(CO)₁₆, Ir₄(CO)₁₂, Co₂(CO)₈, or Ni(CO)₄.

28. The method of claim 15, wherein the metal carbonyl compound comprises Co₂(CO)₈.

29. The method of claim 15, wherein the metal carbonyl compound comprises [Co(CO)₄]⁻

, [Ti(CO)₆]²⁻

, [V(CO)₆]⁻

, [Rh(CO)₄]⁻

, [Fe(CO)₄]²⁻

, [Ru(CO)₄]²⁻

, [Os(CO)₄]²⁻

, [Cr₂(CO)₁₀]²⁻

, [Fe₂(CO)₈]²⁻

, [Tc(CO)₅]⁻

, [Re(CO)₅]⁻

, or [Mn(CO)₅]⁻

.

30. The method of claim 15, wherein the metal carbonyl compound comprises [Co(CO)₄]⁻

.

31. A method for producing polypropiolactone, comprising:

contacting ethylene oxide with carbon monoxide in the presence of a metal carbonyl compound supported on a solid support in a first reaction zone;

carbonylating at least a portion of the ethylene oxide in the first reaction zone to produce beta-propiolactone;

directing the beta-propiolactone to a second reaction zone; and

converting at least a portion of the beta-propiolactone in the second reaction zone to polypropiolactone in the presence of a catalyst, wherein the conversion of the beta-propiolactone to the polypropiolactone is performed in a continuous flow format.

32. The method of claim 31, further comprising isolating the polypropiolactone from the second reaction zone.

33. The method of claim 31, wherein the solid support comprises a polymeric support.

34. The method of claim 33, wherein the polymeric support comprises polystyrene, divinylbenzene, polyvinylpyridine, polymethylmethacrylate, a polyolefin, or polytetrafluoroethylene, or any combinations thereof.

35. The method of claim 31, wherein the solid support comprises an inorganic solid.

36. The method of claim 31, wherein the solid support comprises silica, glass, zirconia, diatomaceous earth, a metal oxide, a metal salt, a ceramic, a clay, a molecular sieve, kieselgur, or titanium dioxide, or any combinations thereof.

37. The method of claim 31, wherein the metal carbonyl compound has a formula [QM_y(CO)_w]^x, wherein:

Q is any ligand or more than one ligand and need not be present;

M is a metal atom;

y is an integer from 1 to 6 inclusive;

w is a number such as to provide the stable metal carbonyl; and

x is an integer from −

3 to +3 inclusive.

38. The method of claim 37, wherein M is Ti, Cr, Mn, Fe, Ru, Co, Rh, Ni, Pd, Cu, Zn, Al, Ga or In.

39. The method of claim 37, wherein M is Co.

40. The method of claim 31, wherein the metal carbonyl compound comprises Ti(CO)₇, V₂(CO)₁₂, Cr(CO)₆, Mo(CO)₆, W(CO)₆, Mn₂(CO)₁₀, Tc₂(CO)₁₀, Re₂(CO)₁₀, Fe(CO)₅, Ru(CO)₅, Os(CO)₅, Ru₃(CO)₁₂, Os₃(CO)₁₂, Fe₃(CO)₁₂, Fe₂(CO)₉, Co₄(CO)₁₂, Rh₄(CO)₁₂, Rh₆(CO)₁₆, Ir₄(CO)₁₂, Co₂(CO)₈, or Ni(CO)₄.

41. The method of claim 31, wherein the metal carbonyl compound comprises Co₂(CO)₈.

42. The method of claim 31, wherein the metal carbonyl compound comprises [Co(CO)₄]⁻

, [Ti(CO)₆]²⁻

, [V(CO)₆]⁻

, [Rh(CO)₄]⁻

, [Fe(CO)₄]²⁻

, [Ru(CO)₄]²⁻

, [Os(CO)₄]²⁻

, [Cr₂(CO)₁₀]²⁻

, [Fe₂(CO)₈]²⁻

, [Tc(CO)₅]⁻

, [Re(CO)₅]⁻

, or [Mn(CO)₅]⁻

.

43. The method of claim 31, wherein the metal carbonyl compound comprises [Co(CO)₄]⁻

.

44. A method for producing an acrylamide, comprising:

contacting ethylene oxide with carbon monoxide in the presence of a metal carbonyl compound supported on a solid support in a first reaction zone;

carbonylating at least a portion of the ethylene oxide in the first reaction zone to produce beta-propiolactone;

directing the beta-propiolactone and an organic amine to a second reaction zone; and

converting at least a portion of the beta-propiolactone and the organic amine in the second reaction zone to an acrylamide, wherein the conversion of the beta-propiolactone and the organic amine to the acrylamide is performed in a continuous flow format.

45. The method of claim 44, further comprising isolating the acrylamide from the second reaction zone.

46. The method of claim 44, wherein the organic amine is ammonia.

47. The method of claim 44, wherein the solid support comprises a polymeric support.

48. The method of claim 47, wherein the polymeric support comprises polystyrene, divinylbenzene, polyvinylpyridine, polymethylmethacrylate, a polyolefin, or polytetrafluoroethylene, or any combinations thereof.

49. The method of claim 44, wherein the solid support comprises an inorganic solid.

50. The method of claim 44, wherein the solid support comprises silica, glass, zirconia, diatomaceous earth, a metal oxide, a metal salt, a ceramic, a clay, a molecular sieve, kieselgur, or titanium dioxide, or any combinations thereof.

51. The method of claim 44, wherein the metal carbonyl compound has a formula [QM_y(CO)_w]^x, wherein:

Q is any ligand or more than one ligand and need not be present;

M is a metal atom;

y is an integer from 1 to 6 inclusive;

w is a number such as to provide the stable metal carbonyl; and

x is an integer from −

3 to +3 inclusive.

52. The method of claim 51, wherein M is Ti, Cr, Mn, Fe, Ru, Co, Rh, Ni, Pd, Cu, Zn, Al, Ga or In.

53. The method of claim 51, wherein M is Co.

54. The method of claim 44, wherein the metal carbonyl compound comprises Ti(CO)₇, V₂(CO)₁₂, Cr(CO)₆, Mo(CO)₆, W(CO)₆, Mn₂(CO)₁₀, Tc₂(CO)₁₀, Re₂(CO)₁₀, Fe(CO)₅, Ru(CO)₅, Os(CO)₅, Ru₃(CO)₁₂, Os₃(CO)₁₂, Fe₃(CO)₁₂, Fe₂(CO)₉, Co₄(CO)₁₂, Rh₄(CO)₁₂, Rh₆(CO)₁₆, Ir₄(CO)₁₂, Co₂(CO)₈, or Ni(CO)₄.

55. The method of claim 44, wherein the metal carbonyl compound comprises Co₂(CO)₈.

56. The method of claim 44, wherein the metal carbonyl compound comprises [Co(CO)₄]⁻

, [Ti(CO)₆]²⁻

, [V(CO)₆]⁻

, [Rh(CO)₄]⁻

, [Fe(CO)₄]²⁻

, [Ru(CO)₄]²⁻

, [Os(CO)₄]²⁻

, [Cr₂(CO)₁₀]²⁻

, [Fe₂(CO)₈]²⁻

, [Tc(CO)₅]⁻

, [Re(CO)₅]⁻

, or [Mn(CO)₅]⁻

.

57. The method of claim 44, wherein the metal carbonyl compound comprises [Co(CO)₄]⁻

.