PROCESS FOR PREPARING ACRYLIC ACID BY A THERMOLYSIS OF POLY-3-HYDROXYPROPIONATE CATALYZED BY AT LEAST ONE MOLECULAR ACTIVE COMPOUND

• US 20140018574A1
• Filed: 07/15/2013
• Published: 01/16/2014
• Est. Priority Date: 07/16/2012
• Status: Abandoned Application

• Current Assignee: BASF SE
• Original Assignee: BASF SE
• Inventors: Pazicky, Marek, Paciello, Rocco, Mueller-Engel, Klaus Joachim, Zurowski, Peter, Fischer, Wolfgang, RAITH, Christian, Brand, Raphael Heinrich, Hartmann, Marco
• Application Number:
  US13/941,856
• Publication Number:
  US 20140018574A1
• Time in Patent Office: Days
• US Class Current: 562/599
• CPC Class Codes: C07C 51/09 from carboxylic acid esters or lactones
• CPC Class Codes: C07C 51/377 by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups C07C51/36 - C07C51/373 take precedence
• CPC Class Codes: C07C 57/04 Acrylic acid; Methacrylic acid

Abstract

A process for preparing acrylic acid by thermolysis of poly-3-hydroxypropionate in the presence of one or more specific tertiary amines as a catalyst.

Claims

1. A process for preparing acrylic acid, comprising:

thermolyzing poly-3-hydroxypropionate in the presence of a catalyst of at least one molecular organic active compound comprising a tertiary nitrogen atom covalently bonded to three different carbon atoms, thereby obtaining the acrylic acid,

wherein

the at least one molecular organic active compound comprises;

no heteroatom other than carbon and hydrogen over and above nitrogen and oxygen,

no nitrogen covalently bonded to one or more hydrogen atoms,

at most one oxygen atom covalently bonded to a hydrogen atom,

no oxygen atom which comprises a covalent double bond to any of the three different carbon atoms, and

neither a radical of an aromatic hydrocarbon nor a radical of a substituted aromatic hydrocarbon, and

the at least one molecular organic active compound has a boiling point of at least 150°

C. and at most 350°

C. at a pressure of 1.0133·

10⁵ Pa, and

a melting point of at most 70°

C. at a pressure of 1.0133·

10⁵ Pa.

2. The process according to claim 1, wherein the at least one molecular organic active compound comprises more than one tertiary nitrogen atom covalently bonded to each of the three different carbon atoms, with the proviso that none of the three different carbon atoms simultaneously comprises a covalent double bond to any oxygen atom.

3. The process according to claim 2, wherein the at least one molecular organic active compound comprises at least two tertiary nitrogen atoms covalently bonded to each of the three different carbon atoms, with the proviso that none of the three different carbon atoms simultaneously comprises a covalent double bond to any oxygen atom.

4. The process according to claim 2, wherein the at least one molecular organic active compound comprises at least three tertiary nitrogen atoms covalently bonded to each of the three different carbon atoms, with the proviso that none of the three different carbon atoms simultaneously comprises a covalent double bond to any oxygen atom.

5. The process according to claim 1, wherein the at least one molecular organic active compound comprises only tertiary nitrogen atoms covalently bonded to each of the three different carbon atoms, with the proviso that none of the three different carbon atoms simultaneously comprises a covalent double bond to any oxygen atom.

6. The process according to claim 1, wherein the at least one molecular organic active compound comprises no oxygen atom covalently bonded to a hydrogen atom.

7. The process according to claim 1, wherein the at least one molecular organic active compound has a boiling point of at least 160°

C. at a pressure of 1.0133·

10⁵ Pa.

8. The process according to claim 1, wherein the at least one molecular organic active compound has a boiling point of at most 345°

C. at a pressure of 1.0133·

10⁵ Pa.

9. The process according to claim 1, wherein the at least one molecular organic active compound has a melting point of at most 60°

C. at a pressure of 1.0133·

10⁵ Pa.

10. The process according to claim 1, wherein the at least one molecular organic active compound has a melting point of at most −

15°

C. at a pressure of 1.0133·

10⁵ Pa.

11. The process according to claim 1, wherein the at least one molecular active compound is selected from the group consisting of pentamethyldiethylenetriamine, N,N,N′

,N′

-tetramethyl-1,6-hexanediamine, bis(2-dimethylaminoethyl)ether, 2,2′

-dimorpholinodiethyl ether, N,N′

-diethylethanolamine, N,N-dimethylcyclohexylamine, N-methylimidazole and 1,2-dimethylimidazole.

12. The process according to claim 1, wherein said thermolyzing, based on a weight of the poly-3-hydroxypropionate, is catalytically effected by 0.01 to 15% by weight of the at least one molecular organic active compound.

13. The process according to claim 1, wherein said thermolyzing, based on a weight of the poly-3-hydroxypropionate, is effected catalytically by up to 50% by weight of the at least one molecular organic active compound.

14. The process according to claim 1, wherein said thermolyzing, based on a weight of the poly-3-hydroxypropionate, is effected catalytically by up to 500% by weight of the at least one molecular organic active compound.

15. The process according to claim 1, wherein said thermolyzing of the poly-3-hydroxypropionate is effected from a solid substance thereof, a melt thereof, a solution thereof in an organic liquid as a solvent, a suspension thereof in the organic liquid as a dispersant, an emulsion thereof in the organic liquid as a dispersant, a biomass thereof, or a slurry of the biomass in an organic solvent as a slurrying agent.

16. The process according to claim 15, wherein the organic liquid has a boiling point of at least 20°

C. above a boiling temperature of acrylic acid at a pressure of 1.0133·

10⁵ Pa.

17. The process according to claim 15, wherein the organic liquid is selected from the group consisting of an ionic liquid, an oligomeric Michael adduct of acrylic acid onto itself and an addition product, dimethyl sulfoxide, N-methyl-2-pyrrolidone, dialkylformamide, a long-chain paraffinic hydrocarbon, a long-chain alkanol, γ

-butyrolactone, ethylene carbonate, diphenyl ether, diglyme, triglyme, tetraglyme, biphenyl, tricresyl phosphate, dimethyl phthalate, diethyl phthalate.

18. The process according to claim 15, wherein a proportion by weight of the poly-3-hydroxypropionate in the solution, the suspension, the emulsion, the biomass, or the slurry of the biomass, is at least 5 to at most 95%.

19. The process according to claim 15, wherein the at least one molecular organic active compound is dissolved in the melt of the poly-3-hydroxypropionate or in the organic liquid.

20. The process according to claim 1, wherein said thermolyzing occurs at a temperature of 50 to 400°

C.

21. The process according to claim 1, wherein the process is performed at, above or below an atmospheric pressure.

22. The process according to claim 1, wherein the acrylic acid is discharged continuously with an aid of a stripping gas.

23. The process according to claim 1, wherein said thermolyzing is effected in the presence of at least one polymerization inhibitor.

24. The process according to claim 1, wherein the poly-3-hydroxypropionate is at least one macromolecular compound comprising a structural section of formula (I),

25. The process according to claim 24, wherein n≦

30 000.

26. The process according to claim 1, wherein the poly-3-hydroxypropionate is a copolymer or a homopolymer.

27. The process according to claim 24, wherein a proportion by weight of the structural section of formula (I) in the poly-3-hydroxypropionate is ≧

40%.

28. The process according to claim 1, wherein the poly-3-hydroxypropionate is obtained by a dehydrating polycondensation of 3-hydroxypropionic acid, a ring-opening polymerization of β

-propiolactone, a carbonylating reaction of ethylene oxide dissolved in a solvent with CO in the presence of at least one cobalt-comprising catalyst, or a biotechnological means in a biological organism.

29. The process according to claim 1, wherein the poly-3-hydroxypropionate has a polydispersity of ≦

2.5.

30. The process according to claim 1, wherein the poly-3-hydroxypropionate has a weight average molecular weight M_w of from 1000 to 2 000 000.

31. The process according to claim 1, wherein the poly-3-hydroxypropionate comprises no vinylic head or end group.

32. The process according to claim 1, wherein the acrylic acid is the obtained by converting acrylic acid-comprising gas phase formed in said thermolyzing to a liquid phase by absorption, condensation, or both.

33. The process according to claim 32, wherein

the acrylic acid is separated from the liquid phase in an elevated purity compared to the liquid phase using at least one thermal separation process, and

the at least one thermal separation process comprises a rectification, a crystallization, or both, of the acrylic acid in the liquid phase.

34. The process according to claim 1, further comprising:

subsequently polymerizing the acrylic acid via a free-radical polymerization, optionally in the presence of a conjugate Brø

nsted base, and optionally in a mixture comprising other mono- or polyunsaturated compounds.

35. The process according to claim 1, wherein the poly-3-hydroxypropionate has a melting point of at most 200°

C. at a pressure of 1.0133·

10⁵ Pa.

36. The process according to claim 1, wherein the poly-3-hydroxypropionate has a melting point of at least 50°

C. at a pressure of 1.0133·

10⁵ Pa.

37. The process according to claim 1, wherein the at least one molecular organic active compound comprises no aromatic ring.