METHOD FOR THE SYNTHESIS OF BIORESOURCED ACRYLIC ACID ESTERS

• US 20110190464A1
• Filed: 07/24/2009
• Published: 08/04/2011
• Est. Priority Date: 07/25/2008
• Status: Abandoned Application

• Current Assignee: Arkema France (Arkema)
• Original Assignee: Arkema France (Arkema)
• Inventors: Dubois, Jean-Luc, Riondel, Alain
• Application Number:
  US13/055,864
• Publication Number:
  US 20110190464A1
• Time in Patent Office: Days
• US Class Current: 526/328
• CPC Class Codes: C07C 219/08 having at least one of the hydroxy groups esterified by a carboxylic acid having the esterifying carboxyl group bound to an acyclic carbon atom of an acyclic unsaturated carbon skeleton
• CPC Class Codes: C07C 45/52 by dehydration and rearrangement involving two hydroxy groups in the same molecule
• CPC Class Codes: C07C 47/22 Acryaldehyde; Methacryaldehyde
• CPC Class Codes: C07C 51/252 of propene, butenes, acrolein or methacrolein
• 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 67/08 by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
• CPC Class Codes: C07C 69/54 Acrylic acid esters; Methacrylic acid esters
• CPC Class Codes: Y02P 20/582 Recycling of unreacted starting or intermediate materials

Abstract

The present invention relates to a method for the synthesis of an acrylic acid ester of formula CH₂═CH—COOR, where R is an alkyl radical having between 1 and 18 carbon atoms and optionally where one of the carbon atoms in the alkyl radical may be replaced with a nitrogen atom. In an embodiment of the invention, glycerol is subjected to a dehydration reaction in the presence of an acid catalyst to obtain acrolein. The acrolein formed is transformed by catalytic oxidation into acrylic acid, which is subjected to an esterification reaction by means of an alcohol of the formula ROH in which R has the meaning as above. The invention also relates to bioresourced esters produced according to the method, and to synthesized polymers using the esters of the invention as polymerization monomers or comonomers.

Claims

1-22. -22. (canceled)

23. A process for synthesizing an acrylic acid ester comprising the steps of:

a) subjecting glycerol to a dehydration reaction in the presence of an acid catalyst to form acrolein;

b) converting the acrolein using catalytic oxidation to form acrylic acid; and

c) esterifying the acrylic acid using an alcohol of formula ROH to form an acrylic acid ester of formula I;

CH₂═

CH—

COOR, wherein R is an alkyl radical having 1 to 18 carbon atoms wherein optionally one of the carbon atoms in the alkyl radical may be replaced with a nitrogen atom.

24. The process of claim 23, wherein step a) comprises a gas phase reaction of the glycerol at a temperature ranging from 150°

C. to 500°

C., and a pressure ranging from 1×

10⁵ Pa to 5×

10⁵ Pa and in the presence of one or more solid acid catalysts having a Hammett acidity of less than +2.

25. The process of claim 23, wherein step b) comprises oxidizing the acrolein at a temperature ranging from 200°

C. to 350°

C., under a pressure ranging from 1×

10⁵ Pa to 5×

10⁵ Pa and in the presence of a solid oxidation catalyst comprising at least one element selected from Mo, V, W, Re, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Te, Sb, Bi, Pt, Pd, Ru or Rh, wherein the at least one element is in metallic form, or oxide, sulfate or phosphate form.

26. The process of claim 23, wherein step c) is carried out at a temperature ranging from 60°

C. to 90°

C. and at a pressure ranging from 1.2×

10⁵ Pa to 2×

10⁵ Pa and in the presence of either i) an acid catalyst in a homogeneous single-phase medium, or ii) a solid acid catalyst in a heterogeneous two-phase medium.

27. The process of claim 23, wherein step c) comprises at least two substeps comprising:

i) reacting the acrylic acid and an alcohol of formula R₀OH to form an acrylic acid ester of formula II;

CH₂═

CH—

COOR₀, wherein R₀ is selected from —

CH₃, —

C₂H₅, —

C₃H₇, or —

C₄H₉, and ii) transesterifying the acrylic acid ester of formula II to form a desired acrylic acid ester of formula I.

28. The process of claim 27, wherein the transesterification is carried out in the presence of a transesterification catalyst and at least one polymerization inhibitor at a temperature ranging from 20°

C. to 120°

C. and at a pressure that is equal to or lower than atmospheric, wherein the transesterification catalyst is selected from one or more of alkyl titanates, tin derivatives, zirconium derivatives, magnesium derivatives, or calcium derivatives.

29. An acrylic acid ester of formula I:

CH₂═

CH—

COOR made by the process of claim 23, wherein R is a linear or branched alkyl radical having from 1 to 18 carbon atoms, wherein optionally one of the carbon atoms in the alkyl radical may be replaced with a nitrogen atom, and wherein the acrylic acid ester of formula I has at least 0.2×

10<sup><

10</sup>% by weight of ¹⁴C based on the total weight of carbon in the ester of formula I.

30. The acrylic acid ester of claim 29, wherein the alcohol ROH used in step c) is bioresourced.

31. The acrylic acid ester of claim 30, wherein the alcohol is n-butanol obtained by aerobic fermentation of biomass in the presence of bacteria.

32. A method of making a polymer or copolymer comprising using as monomers or comonomers in a polymerization reaction one or more acrylic acid esters of claim 23.

33. A polymer or copolymer made by the process of claim 32.

34. A process for synthesizing an acrylic acid ester of formula CH₂═

CH—

COO—

CH₂—

CH(C₂H₅)—

(CH₂)₃—

CH₃ comprising the steps of

a) subjecting glycerol to a dehydration reaction in the presence of an acid catalyst to form acrolein;

b) converting the acrolein using catalytic oxidation to form acrylic acid; and

c) esterifying the acrylic acid under acid catalysis and using an alcohol of formula CH₃—

(CH₂)₃—

CH(C₂H₅)—

CH₂OH.

35. The process of claim 34, wherein step a) comprises a gas phase reaction at a temperature ranging from 150°

C. to 500°

C., and at a pressure ranging from 1×

10⁵ Pa to 5×

10⁵ Pa in the presence of one or more solid acid catalysts having a Hammett acidity of less than +2.

36. The process of claim 34, wherein step b) is carried out at a temperature ranging from 200°

C. to 350°

C., and at a pressure ranging from 1×

10⁵ Pa to 5×

10⁵ Pa and in the presence of a solid oxidation catalyst comprising at least one element selected from Mo, V, W, Re, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Te, Sb, Bi, Pt, Pd, Ru or Rh, wherein the at least one element is present in metallic form, or in oxide, sulfate or phosphate form.

37. The process of claim 34, wherein the step c) esterification is carried out at a temperature ranging from 60°

C. to 90°

C. and at a pressure ranging from 1.2×

10⁵ Pa to 2×

10⁵ Pa and either in the presence of i) an acid catalyst in a homogeneous single-phase medium, or ii) a solid acid catalyst in a heterogeneous two-phase medium.

38. An acrylic acid ester of formula CH₂═

CH—

COO—

CH₂—

CH(C₂H₅)—

(CH₂)₃—

CH₃ made by the process of claim 34, wherein the ester comprises at least 0.2×

10<sup>−

10</sup>% by weight of ¹⁴C, based on the total weight of carbon in the ester.

39. A process for synthesizing an acrylic acid amino ester of formula CH₂═

CH—

COO—

CH₂—

CH₂—

N(CH₃)₂ comprising the steps of;

a) subjecting glycerol to a dehydration reaction in the presence of an acid catalyst to form acrolein;

b) converting the acrolein by oxidation to form acrylic acid;

c) esterifying the acrylic acid using an alcohol of formula R₀OH, wherein R₀ is selected from —

CH₃,—

C₂H₅, —

C₃H₇, or —

C₄H₉, to form an ester; and

d) transesterifying the ester formed in step c) using an amino alcohol of formula (CH₃)₂—

N—

CH₂—

CH₂OH to form the acrylic acid amino ester.

40. The process of claim 39, wherein step a) comprises a gas phase reaction conducted at a temperature ranging from 150°

C. to 500°

C., and at a pressure ranging from 1×

10⁵ Pa to 5×

10⁵ Pa in the presence of one or more solid acid catalysts having a Hammett acidity of less than +2.

41. The process of claim 39, wherein step h) is carried out at a temperature ranging from 200°

C. to 350°

C., at a pressure ranging from 1×

10⁵ Pa to 5×

10⁵ Pa, and in the presence of a solid oxidation catalyst comprising at least one element selected from Mo, V, W, Re, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Te, Sb, Bi, Pt, Pd, Ru or Rh, wherein the at least one element is present in metallic form, or in oxide, sulfate or phosphate form.

42. The process of claim 39, wherein R₀ of step c) is selected from —

CH₃, —

C₂H₅, —

C₃H₇ or —

C₄H₉, and wherein the esterification of step c) is conducted at a temperature ranging from 60°

C. to 90°

C., at a pressure ranging from 1.2×

10⁵ Pa to 2×

10⁵ Pa and in the presence of either i) an acid catalyst in a homogeneous single-phase medium, or ii) a solid acid catalyst in a heterogeneous two-phase medium.

43. The process of claim 39, wherein the transesterification of step d) is carried out in the presence of a transesterification catalyst and at least one polymerization inhibitor at a temperature ranging from 20°

C. to 120°

C., at a pressure that is equal to or lower than atmospheric pressure, wherein the transesterification catalyst is selected from one or more of alkyl titanates, tin derivatives, zirconium derivatives, magnesium derivatives, or calcium derivatives.

44. An acrylic acid amino ester of formula CH₂═

CH—

COO—

CH₂—

CH₂—

N(CH₃)₂ made by the process of claim 39, wherein the acrylic acid amino ester comprises at least 0.2×

10<sup>−

10</sup>% by weight of ¹⁴C, based on the total weight of carbon in the acrylic acid amino ester.