Claims
- 1. A method, comprising:
hydrogenolyzing a PHA to form a diol.
- 2. The method of claim 1, wherein the PHA is hydrogenolyzed at a temperature of at least about 100° C.
- 3. The method of claim 1, wherein the percent yield of diol from the PHA is at least about five percent.
- 4. The method of claim 1, wherein the PHA is a chiral PHA, and a percent chirality yield of chiral diol is at least about five percent.
- 5. The method of claim 1, wherein hydrogenolysis occurs in the presence of a hydrogen-containing gas.
- 6. The method of claim 5, wherein the hydrogen-containing gas comprises hydrogen gas.
- 7. The method of claim 1, wherein the PHA is derived from a biomass.
- 8. The method of claim 7, wherein the biomass is selected from the group consisting of plant biomass and microbial biomass.
- 9. The method of claim 7, wherein the biomass is non-lyophilized.
- 10. The method of claim 7, wherein less than about 50 weight percent of the PHA that is treated to form the diol is removed from the biomass before being treated to form the diol.
- 11. The method of claim 1, further comprising contacting the PHA with a reducing agent during hydrogenolysis.
- 12. The method of claim 1, further comprising contacting the PHA with a catalyst during hydrogenolysis.
- 13. The method of claim 1, further comprising combining the PHA with a solvent.
- 14. The method of claim 1, wherein the diol has the structure:
- 15. The method of claim 14, wherein n is zero, one or two.
- 16. The method of claim 15, wherein R2, R3 and R4 are each hydrogen atoms.
- 17. The method of claim 16, wherein R1 is selected from the group consisting of a hydrogen atom, a methyl radical, an ethyl radical, a propyl radical, a butyl radical and a pentyl radical.
- 18. The method of claim 1, wherein the PHA is selected from the group consisting of poly 3-hydroxybutyrate, poly 3-hydroxypropionate, poly 4-hydroxybutyrate, poly 5-hydroxypentanoate and poly 6-hydroxyhexanoate.
- 19. The method of claim 1, wherein the diol is selected from the group consisting of 1,4-butanediol, 1,3-propanediol, 1,3-butanediol, 1,6-hexanediol, 1,3-pentanediol, 1,3-hexanediol, 1,3-octanediol and 1,2-propanediol.
- 20. The method of claim 1, wherein the PHA is contacted with the transition metal catalyst in the substantial absence of a halogenated solvent.
- 21. The method of claim 1, wherein the diol is formed without first forming a hydroxy acid.
- 22. The method of claim 1, wherein the diol contains only one monomer unit from the PHA.
- 23. The method of claim 13, wherein the solvent comprises an alcohol.
- 24. The method of claim 23, wherein the alcohol comprises a diol.
- 25. The method of claim 24, wherein the diol comprises the same diol as formed by treating the PHA.
- 26. The method of claim 24, further comprising reacting the diol to form a cyclic ether.
- 27. The method of claim 26, wherein the cyclic ether comprises polyether polyol.
- 28. The method of claim 1, wherein the PHA comprises a monomer unit selected from the group consisting of 3-hydroxybutyrate, 3-hydroxypropionate, 4-hydroxybutyrate, 5-hydroxypentanoate and 6-hydroxyhexanoate.
- 29. A method, comprising:
treating a biomass containing a PHA to form a PHA intermediate; and removing at least about 10 weight percent of the PHA intermediate from the biomass.
- 30. The method of claim 29, wherein at least about 20 weight percent of the intermediate is removed from the biomass.
- 31. The method of claim 29, wherein at least about 30 weight percent of the PHA intermediate is removed from the biomass.
- 32. The method of claim 29, wherein at least about 40 weight percent of the PHA intermediate is removed from the biomass.
- 33. The method of claim 29, wherein, before treating the PHA, the biomass is non-lyophilized.
- 34. The method of claim 29, wherein the biomass is selected from the group consisting of plant biomass and microbial biomass.
- 35. The method of claim 29, wherein less than about 50 weight percent of the PHA that is treated to form the ester is removed from the biomass before being treated to form the ester.
- 36. The method of claim 29, further comprising, before treating the PHA to form the ester, removing at least about 60 weight percent of the PHA that is treated to form the ester from the biomass.
- 37. The method of claim 29, wherein the PHA intermediate contains at most 50 monomer units from the PHA.
- 38. The method of claim 29, wherein the PHA intermediate contains only one monomer unit from the PHA.
- 39. The method of claim 29, wherein the intermediate is selected from the group consisting of esters, amides, diols and alkenoic acids.
- 40. The method of claim 29, wherein the PHA is a chiral PHA, and a percent chirality yield of chiral PHA intermediate is at least about five percent.
- 41. The method of claim 29, wherein the percent yield of alkenoic byproducts is less than about 10%.
- 42. The method of claim 29, wherein the PHA is selected from the group consisting of poly 3-hydroxybutyrate, poly 3-hydroxypropionate, poly 4-hydroxybutyrate, poly 5-hydroxypentanoate and poly 6-hydroxyhexanoate.
- 43. The method of claim 29, wherein the PHA is a copolymer, and the method forms multiple PHA intermediates.
- 44. The method of claim 29, wherein treating the PHA includes heating the PHA to a temperature of at least about 100° C.
- 45. The method of claim 29, wherein the PHA is combined with a solvent.
- 46. The method of claim 29, wherein treating the PHA is performed at a pressure of at least about 50 psig.
- 47. The method of claim 29, wherein treating the PHA occurs in a combination that contains less than about one milliliter of solvent other than the alcohol per gram of the PHA.
- 48. The method of claim 29, wherein the PHA comprises a monomer unit selected from the group consisting of 3-hydroxybutyrate, 3-hydroxypropionate, 4-hydroxybutyrate, 5-hydroxypentanoate and 6-hydroxyhexanoate.
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority under 35 U.S.C. §119(e)(1) to U.S. Provisional Patent Application Serial No. 60/341,546, filed Dec. 18, 2001, and entitled “Process of Making Chemical Intermediates from Naturally Occurring Polyhydroxyalkanoates,” and to U.S. Provisional Patent Application Serial No. 60/402,469, filed Aug. 9, 2002, and entitled “Alkanoic and Alkenoic Acid Esters and Methods of Making Same,” both of which are incorporated by reference.
Provisional Applications (2)
|
Number |
Date |
Country |
|
60341546 |
Dec 2001 |
US |
|
60402469 |
Aug 2002 |
US |