Process for beta-lactone production

1. A method comprising steps of:

reacting the contents of a feed stream comprising an epoxide, a solvent, a carbonylation catalyst and carbon monoxide to produce a reaction product stream comprising a beta-lactone;

separating at least a portion of the beta-lactone in the reaction product stream from the solvent and carbonylation catalyst to produce:

i) a beta-lactone stream comprising beta-lactone, and

ii) a catalyst recycling stream comprising carbonylation catalyst and solvent; and

adding the catalyst recycling stream to the feed stream.

2. The method of claim 1 , further comprising treating the beta-lactone stream under conditions to convert the beta lactone into a compound selected from the group consisting of: acrylic acid; acrylates; acrylamide; and polyacrylates.

3. The method of claim 1 , wherein the reaction product stream comprises a portion of the epoxide.

4. The method of claim 3 , wherein the reaction product stream comprises sufficient epoxide to prevent anhydride formation.

5. The method of claim 1 , wherein the separating step comprises exposing the reaction product stream to reduced pressure.

6. The method of claim 1 , wherein the separating step comprises exposing the reaction product stream to elevated temperature.

7. The method of claim 1 , wherein the boiling point of the solvent is at least 20° C. higher than the boiling point of the beta lactone.

8. The method of claim 1 , wherein the epoxide has the formula

where, R 1 and R 2 , are each independently selected from the group consisting of: —H; optionally substituted C 1-6 aliphatic; optionally substituted phenyl; optionally substituted C 1-6 heteroaliphatic; optionally substituted 3- to 6-membered carbocycle; and optionally substituted 3- to 6-membered heterocycle,

where R 1 and R 2 can optionally be taken together with intervening atoms to form a 3- to 6-membered, substituted or unsubstituted ring optionally containing one or more heteroatoms.

9. The method of claim 1 , wherein the epoxide is chosen from the group consisting of: ethylene oxide; propylene oxide; 1,2-butylene oxide; 2,3-butylene oxide; epichlorohydrin; cyclohexene oxide; cyclopentene oxide; 3,3,3-Trifluoro-1,2-epoxypropane, styrene oxide; a glycidyl ether; and a glycidyl ester.

10. The method of claim 1 , wherein the epoxide comprises ethylene oxide.

11. The method of claim 1 , wherein the epoxide comprises propylene oxide.

12. The method of claim 2 , wherein the treating step is performed in the presence of a compound selected from the group consisting of: an alcohol, an amine and a thiol, under conditions that produce the corresponding acrylic ester, acrylamide, or a thioacrylate respectively.

13. The method of claim 2 , wherein the treating step is performed in the presence of a compound of formula H—Y to afford an acrylate having the formula

wherein, R 1 and R 2 , are each independently selected from the group consisting of: —H, optionally substituted C 1-6 aliphatic, optionally substituted C 1-6 heteroaliphatic, optionally substituted 3- to 12-membered carbocycle, and optionally substituted 3- to 12-membered heterocycle, or R 1 and R 2 can optionally be taken together with intervening atoms to form an optionally substituted ring optionally containing one or more heteroatoms;

wherein, Y is selected from the group consisting of OR 13 , NR 11 R 12 and SR 13 ;

wherein, R 11 , R 12 , and R 13 are independently selected from the group consisting of: —H; optionally substituted C 1-32 aliphatic, optionally substituted C 1-32 heteroaliphatic, optionally substituted 3- to 14-membered carbocycle, and optionally substituted 3- to 14-membered heterocycle, or R 11 and R 12 can optionally be taken together with intervening atoms to form an optionally substituted ring optionally containing one or more heteroatoms.

14. The method of claim 1 , wherein the carbonylation catalyst comprises a metal carbonyl compound.

15. The method of claim 14 , wherein the metal carbonyl compound has the general formula [QM y (CO) w ] x ,

where:

Q is any 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.

16. The method of claim 2 , wherein the treating step is mediated by a catalyst.

17. The method of claim 16 , wherein the catalyst in the treating step is an acid catalyst.

18. The method of claim 16 , wherein the catalyst in the treating step is a basic catalyst.

19. The method of claim 1 , wherein the carbon monoxide in the reacting step is supplied as an industrial gas stream comprising carbon monoxide and one or more additional gases.

20. A method comprising steps of:

reacting the contents of a feed stream comprising an epoxide, a solvent, a carbonylation catalyst and carbon monoxide to produce a reaction product stream comprising a beta-lactone;

returning the entirety of the reaction product stream to the feed stream until the weight percent of beta-lactone in the reaction product stream is in a predetermined range;

then separating at least a portion of the beta-lactone in the reaction product stream from the solvent and carbonylation catalyst to produce:

i) a beta-lactone stream comprising beta-lactone, and

ii) a catalyst recycling stream comprising the carbonylation catalyst and the solvent; and

adding the catalyst recycling stream to the feed stream.

21. The method of claim 1 , further comprising treating the beta-lactone stream under conditions to convert the beta lactone into a compound selected from the group consisting of: acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate.

22. The method of claim 1 , further comprising treating the beta-lactone stream under conditions to convert the beta lactone into acrylic acid.

23. The method of claim 1 , further comprising treating the beta-lactone stream under conditions to convert the beta lactone into methyl acrylate.

24. The method of claim 1 , further comprising treating the beta-lactone stream under conditions to convert the beta lactone into ethyl acrylate.

25. The method of claim 1 , further comprising treating the beta-lactone stream under conditions to convert the beta lactone into n-butyl acrylate.

26. The method of claim 1 , further comprising treating the beta-lactone stream under conditions to convert the beta lactone into isobutyl acrylate.

27. The method of claim 1 , further comprising treating the beta-lactone stream under conditions to convert the beta lactone into 2-ethylhexyl acrylate.

28. The method of claim 1 , wherein the solvent has a boiling point higher than the boiling point of the beta-lactone, at the same pressure.

29. The method of claim 1 , wherein at least a portion of the solvent has a boiling point lower than the boiling point of the beta-lactone, at the same pressure.

30. The method of claim 1 , wherein the beta-lactone stream comprises a portion of the solvent.

31. The method of claim 1 , wherein the beta-lactone stream comprises a portion of the epoxide.

32. The method of claim 1 , wherein the catalyst recycling stream comprises beta-lactone.

33. The method of claim 3 , wherein the reaction product stream comprises at least about 5% epoxide.

34. The method of claim 3 , wherein the reaction product stream comprises at least about 3% epoxide.

35. The method of claim 3 , wherein the reaction product stream comprises at least about 0.1% epoxide.

36. The method of claim 1 , wherein the reaction product stream comprises less than about 5% anhydride.

37. The method of claim 1 , wherein the reaction product stream comprises less than about 1% anhydride.

38. The method of claim 1 , further comprising treating the catalyst recycling stream, prior to the adding step by performing at least one step selected from the group consisting of: adding fresh carbonylation catalyst, removing spent carbonylation catalyst; adding solvent; adding epoxide, adding a portion of the beta-lactone stream; and any combination of two or more of these.

39. The method of claim 1 , wherein the separating step comprises volatilizing at least a portion of the beta-lactone from the reaction product stream.

40. The method of claim 5 , wherein the reduced pressure is between about 5 Torr and about 500 Torr.

41. The method of claim 5 , wherein the reduced pressure is between about 10 Torr and about 100 Torr.

42. The method of claim 6 , wherein the elevated temperature is greater than the boiling point of the beta-lactone but less than the boiling point of the solvent.

43. The method of claim 39 , wherein the separating step comprises exposing the reaction product stream to reduced pressure and elevated temperature.

44. The method of claim 1 , further comprising adding beta-lactone to the feed stream.

45. The method of claim 44 , wherein the beta-lactone added to the feed stream comprises a portion of the beta-lactone stream.

46. The method of claim 45 , wherein the beta-lactone stream is added to the feed until the weight percent of beta-lactone in the reaction product stream is in the range of about 10% to about 90%, then withdrawing a portion of the beta-lactone stream as a product to maintain the weight percent of beta-lactone in the reaction product stream in the range of about 10% to about 90%.

47. The method of claim 45 , wherein the beta-lactone stream is added to the feed until the weight percent of beta-lactone in the reaction product stream is in the range of about 30% to about 65%, then withdrawing a portion of the beta-lactone stream as a product to maintain the weight percent of beta-lactone in the reaction product stream in the range of about 30% to about 65%.

48. The method of claim 45 , wherein the beta-lactone stream is added to the feed until the weight percent of beta-lactone in the reaction product stream is in the range of about 43% to about 53%, then withdrawing a portion of the beta-lactone stream as a product to maintain the weight percent of beta-lactone in the reaction product stream in the range of about 43% to about 53%.

49. The method of claim 2 , further comprising adding a second solvent to the beta lactone prior to the treating step.

50. The method of claim 2 , wherein the treating step is performed in the gas phase.

51. The method of claim 1 , wherein the boiling point of the solvent is between about 20 and about 80° C. higher than the boiling point of the beta-lactone.

52. The method of claim 1 , wherein the boiling point of the solvent is about 30 to about 60° C. higher than the boiling point of the beta lactone.

53. The method of claim 1 , wherein the feed stream comprises ethylene oxide and a high boiling solvent that has a boiling point of at least 172° C. at atmospheric pressure; and the reaction product stream contains beta-propiolactone.

54. The method of claim 1 , wherein the feed stream comprises propylene oxide and a high boiling solvent that has a boiling point of at least 180° C. at atmospheric pressure; and the reaction product stream contains beta-butyrolactone.

55. The method of claim 1 , wherein the solvent is selected from the group consisting of: esters; ethers; sulfolane; cyclic carbonates; imidazolidinones; and pyrolidones.

56. The method of claim 1 , wherein the solvent is selected from the group consisting of: sulfolane; N-methyl pyrrolidone; 1,3-Dimethyl-2-imidazolidinone; diglyme; triglyme; tetraglyme; ethylene carbonate; propylene carbonate; dibasic esters; THF; THF modified with a C 1-32 aliphatic; and mixtures of any two or more of these.

57. The method of claim 56 , wherein the solvent comprises THF.

58. The method of claim 56 , wherein the solvent comprises sulfolane.

59. The method of claim 56 , wherein the solvent comprises a dibasic ester.

60. The method of claim 56 , wherein the solvent comprises a mixture of sulfolane and THF.

61. The method of claim 56 , wherein the solvent comprises a mixture of sulfolane and THF modified with a C 1-32 aliphatic.

62. The method of claim 56 , wherein the modified THF has the form:

wherein, R is selected from the group consisting of: optionally substituted aliphatic; optionally substituted acyl, optionally substituted aromatic, and polyether.

63. The method of claim 56 , wherein the solvent further comprises isosorbide dimethyl ether.

64. The method of claim 53 , wherein the feed stream comprises sulfolane.

65. The method of claim 54 , wherein the feed stream comprises sulfolane.

66. The method of claim 53 , wherein the feed stream comprises one of THF, and THF modified with a C 1-32 aliphatic.

67. The method of claim 54 , wherein the feed stream comprises one of THF, and THF modified with a C 1-32 aliphatic.

68. The method of claim 53 , wherein the feed stream comprises a dibasic-ester.

69. The method of claim 54 , wherein the feed stream comprises a dibasic-ester.

70. The method of claim 1 , wherein the reacting step is performed in adiabatic reactor.

71. The method of claim 70 , wherein the adiabatic reactor is a tubular reactor.

72. The method of claim 1 , wherein the reacting step is performed at a pressure from about 50 psi to about 5000 psi.

73. The method of claim 1 , wherein the reacting step is performed at a pressure from about 50 psi to about 2000 psi.

74. The method of claim 1 , wherein the reacting step is performed at a pressure from about 200 psi to about 1000 psi.

75. The method of claim 1 , wherein the reacting step is performed at a pressure from about 200 psi to about 600 psi.

76. The method of claim 1 , wherein the reacting step is performed at a temperature from about 0° C. to about 125° C.

77. The method of claim 1 , wherein the reacting step is performed at a temperature from about 30° C. to about 100° C.

78. The method of claim 1 , wherein the reacting step is performed at a temperature from about 40° C. to about 80° C.

79. The method of claim 19 , wherein the industrial gas stream comprises syngas.

80. The method of claim 1 , wherein the carbon monoxide in the reacting step is supplied in substantially pure form.

81. The method of claim 1 , wherein the beta-lactone stream comprises unreacted epoxide.

82. The method of claim 1 , wherein the beta-lactone stream comprises carbon monoxide.

83. The method of claim 1 , wherein the beta-lactone stream comprises solvent.

84. The method of claim 81 , wherein the epoxide, carbon monoxide or solvent are returned to the feed stream.

85. The method of claim 82 , wherein the epoxide, carbon monoxide or solvent are returned to the feed stream.

86. The method of claim 83 , wherein the epoxide, carbon monoxide or solvent are returned to the feed stream.

87. The method of claim 84 , wherein a portion of the beta-lactone stream is returned to the feed.

88. The method of claim 85 , wherein a portion of the beta-lactone stream is returned to the feed.

89. The method of claim 86 , wherein a portion of the beta-lactone stream is returned to the feed.

90. The method of claim 20 , wherein the reaction product stream is returned to the feed until the weight percent of beta-lactone in the reaction product stream is in the range of about 10% to about 90%, then withdrawing a portion of the beta-lactone stream as a product to maintain the weight percent of beta-lactone in the reaction product stream in the range of about 10% to about 90%.

91. The method of claim 20 , wherein the reaction product stream is returned to the feed until the weight percent of beta-lactone in the reaction product stream is in the range of about 30% to about 65%, then withdrawing a portion of the beta-lactone stream as a product to maintain the weight percent of beta-lactone in the reaction product stream in the range of about 30% to about 65%.

92. The method of claim 20 , wherein the reaction product stream is returned to the feed until the weight percent of beta-lactone in the reaction product stream is in the range of about 43% to about 53%, then withdrawing a portion of the beta-lactone stream as a product to maintain the weight percent of beta-lactone in the reaction product stream in the range of about 43% to about 53%.