Process for production of acrylates from epoxides

Patent metadata

Field	Value
Publication number	US-9914689-B2
Application number	US-201615291011-A
Country	US
Kind code	B2
Filing date	Oct 11, 2016
Priority date	Oct 26, 2011
Publication date	Mar 13, 2018
Grant date	Mar 13, 2018

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.

First claim

The invention claimed is:

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 , V 2 (CO) 12 , Cr(CO) 6 , Mo(CO) 6 , W(CO) 6 , Mn 2 (CO) 10 , Tc 2 (CO) 10 , Re 2 (CO) 10 , Fe(CO) 5 , Ru(CO) 5 , Os(CO) 5 , Ru 3 (CO) 12 , Os 3 (CO) 12 , Fe 3 (CO) 12 , Fe 2 (CO) 9 , Co 4 (CO) 12 , Rh 4 (CO) 12 , Rh 6 (CO) 16 , Ir 4 (CO) 12 , Co 2 (CO) 8 , or Ni(CO) 4 .

12. The method of claim 1 , wherein the metal carbonyl compound comprises Co 2 (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− , [Cr 2 (CO) 10 ] 2− , [Fe 2 (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 , V 2 (CO) 12 , Cr(CO) 6 , Mo(CO) 6 , W(CO) 6 , Mn 2 (CO) 10 , Tc 2 (CO) 10 , Re 2 (CO) 10 , Fe(CO) 5 , Ru(CO) 5 , Os(CO) 5 , Ru 3 (CO) 12 , Os 3 (CO) 12 , Fe 3 (CO) 12 , Fe 2 (CO) 9 , Co 4 (CO) 12 , Rh 4 (CO) 12 , Rh 6 (CO) 16 , Ir 4 (CO) 12 , Co 2 (CO) 8 , or Ni(CO) 4 .

28. The method of claim 15 , wherein the metal carbonyl compound comprises Co 2 (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− , [Cr 2 (CO) 10 ] 2− , [Fe 2 (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 polyst

Assignees

• Novomer Inc

Inventors

• Porcelli Richard V
• Farmer Jay J
• Lapointe Robert E

Classifications

• C07C51/09 Primary

  from carboxylic acid esters or lactones · CPC title

• C07C67/03

  by reacting an ester group with a hydroxy group · CPC title

• C07C51/12

  on an oxygen-containing group in organic compounds, e.g. alcohols · CPC title

• C08G63/823

  for the preparation of polylactones or polylactides · CPC title

• C07D305/12

  Beta-lactones · CPC title