Processes for producing 2,5-furandicarboxylic acid and derivatives thereof and polymers made therefrom

Patent metadata

Field	Value
Publication number	US-10538499-B2
Application number	US-201615564590-A
Country	US
Kind code	B2
Filing date	Apr 13, 2016
Priority date	Apr 14, 2015
Publication date	Jan 21, 2020
Grant date	Jan 21, 2020

Abstract

An integrated process is described for producing 2,5-furandicarboxylic acid and/or a derivative thereof from a six carbon sugar-containing feed, comprising: a) dehydrating a feed comprising a six-carbon sugar unit, in the presence of a bromine source and of a solvent, to generate an oxidation feed comprised of at least one of 5-hydroxymethylfurfural and/or a derivative or derivatives of 5-hydroxymethylfurfural in the solvent, together with at least one bromine containing species; b) contacting the oxidation feed from step (a) with a metal catalyst and with an oxygen source under oxidation conditions to produce an oxidation product mixture comprising 2,5-furandicarboxylic acid (FDCA) and/or a derivative thereof, the solvent, and a residual catalyst; c) purifying and separating the mixture obtained in step (b) to obtain FDCA and/or a derivative thereof and the solvent; and d) recycling at least a portion of the solvent obtained in step (c) to step (a).

First claim

The invention claimed is:

1. An integrated process for producing 2,5-furandicarboxylic acid and/or a derivative thereof from a six carbon sugar-containing feed, comprising:
a) dehydrating a feed comprising a six-carbon sugar unit, in the presence of a bromine source and of a solvent, at an elevated temperature and for a time sufficient to generate an oxidation feed comprised of at least one of 5-hydroxymethylfurfural and/or a derivative or derivatives of 5-hydroxymethylfurfural in the solvent, together with at least one bromine containing species;
b) contacting the oxidation feed from step (a) with a homogeneous metal catalyst based on Co and Mn and with an oxygen source at an elevated temperature for a time sufficient to produce an oxidation product mixture comprising 2,5-furandicarboxylic acid (FDCA) and/or a derivative thereof, the solvent, and a residual catalyst;
c) purifying and separating the mixture obtained in step (b) to obtain FDCA and/or a derivative thereof and the solvent; and
d) recycling at least a portion of the solvent obtained in step (c) to step (a),
wherein each optionally present derivative is at least one selected from the group consisting of diacid, diether, diester, ether-acid, ether-ester, ester-acid, ester-aldehyde, ether-aldehyde, ether-acetal, ester-acetal, acetal-acid, alcohol-acid, alcohol-ester, alcohol-acetal, diol, diacetal, and aldehyde-acetal.

2. A process according to claim 1 , further comprising regulating the amount of bromine in step (b) by adding to or removing bromine containing species from the oxidation feed prior to step (b).

3. A process according to claim 1 or claim 2 , wherein the bromine containing species in the oxidation feed comprise one or more of an inorganic bromide and organic bromide.

4. A process according to claim 1 , wherein the metal catalyst comprises one or more transition metals.

5. A process according to claim 1 , wherein the metal catalyst comprises cobalt (II) acetate tetrahydrate, and manganese (II) acetate tetrahydrate.

6. A process according to claim 1 , wherein the metal catalyst further comprises Zr.

7. A process according to claim 1 , wherein the metal catalyst further comprises Ce.

8. A process according to claim 1 , wherein the bromine source comprises hydrogen bromide.

9. A process according to claim 1 , wherein the feed to the dehydration step comprises one or more of starch, amylose, galactose, cellulose, hemicellulose, inulin, fructan, glucose, fructose, sucrose, maltose, cellobiose, lactose, and sugar oligomers.

10. A process according to claim 1 , wherein the solvent comprises acetic acid or a mixture of acetic acid and water.

11. A process according to claim 1 , wherein the feed is dehydrated in the further presence of a C 1 -C 5 alcohol.

12. A process according to claim 1 , further comprising regulating the water content of the feed to the dehydration step and/or to the oxidation step.

13. A process according to claim 1 , wherein the oxidation step is performed at a temperature of from about 120 to about 250 degrees Celsius and at an oxygen partial pressure of from about 0.02 to about 100 bar.

14. A process according to claim 1 , further comprising recycling bromine in the form of one or more bromine sources after the oxidation step back to the dehydration step.

15. A process according to claim 1 , further comprising esterifying 2,5-furandicarboxylic acid with a C 1 -C 12 aliphatic alcohol or a C 1 -C 12 aliphatic diol, under conditions effective for carrying out the esterification and optionally in the presence of a suitable esterification catalyst.

16. A process according to claim 1 , further comprising preparing a polyester by transesterification of at least one ester of 2,5-furandicarboxylic acid with a C 2 to C 12 aliphatic diol or a polyol and optionally at least one of a polyalkylene ether glycol (PAEG), a polyfunctional acid or a polyfunctional hydroxyl acid.

17. A process according to claim 15 , further comprising preparing a semi-crystalline prepolymer of isoidide with a 2,5-furandicarboxylic acid ester and optionally 1,4-butanediol or 2,3-butanediol by melt polymerization, then performing solid state post condensation on the semi-crystalline prepolymer.

18. The process according to claim 1 , further comprising preparing a furan based polyamide composition comprising contacting an aliphatic or aromatic diamine with the 2,5-furandicarboxylic acid and/or one or more derivatives thereof, optionally in the presence of a solvent.

19. The process according to claim 1 , further comprising:
e) dissolving an aromatic diamine monomer in a polar solvent to form a diamine solution under inert atmosphere, wherein the solvent is selected from the group consisting of dimethyl acetamide, dimethyl formamide and dimethyl sulfoxide, and wherein the aromatic diamine comprises m-phenylene diamine;
f) adding an aromatic diacid monomer or aromatic diacid derivative component in the form of the 2,5-furandicarboxylic acid derivative thereof to the diamine solution at a temperature in the range of −5 to 35 degrees Celsius to form a reaction mixture;
g) continuing the reaction until there is no further increase in temperature or until a final viscosity of the reaction mixture is achieved; and
h) isolating a furan-based polyamide polymer from the reaction mixture.

20. An integrated process for producing from a six-carbon sugar-containing feed 2,5-furandicarboxylic acid and/or a derivative thereof, and optionally co-producing at least one of furan-2,5-dimethanol, (tetrahydrofuran-2,5-diyl) dimethanol, a derivative of furan- 2 , 5 -dimethanol, and a derivative of (tetrahydrofuran-2,5-diyl) dimethanol, comprising:
a) dehydrating a feed comprising a six-carbon sugar unit in the presence of a solvent, at an elevated temperature and for a time sufficient to provide a dehydration product including at least one of 5-hydroxymethylfurfural and/or a derivative or derivatives of 5-hydroxymethylfurfural in the solvent;
b) hydrogenating at least a portion of the at least one of hydroxymethylfurfural and/or a derivative or derivatives of 5-hydroxymethylfurfural to form reduced derivatives therefrom, by combining at least a portion of the dehydration product with hydrogen; and
c) oxidizing a portion of the dehydration product not hydrogenated, if any, and optionally including oxidizing at least a portion of the reduced derivatives from step b), by combination with an oxygen source in the presence of a metal catalyst at an elevated temperature and for a time sufficient to produce a mixture comprising an oxidation product comprising 2,5-furandicarboxylic acid (FDCA) and/or a derivative thereof, the solvent and a residual catalyst;
d) purifying and separating the mixture obtained in step c) to obtain FDCA and/or a derivative thereof and the solvent; and
e) recycling at least a portion of the solvent obtained in step d) to step a);
wherein either or both of steps a) and b) are carried out in the presence of a bromine source so that a bromine-containing species, a reduced bromine-containing species or both are included in the dehydration product and/or the reduced derivatives fed to the oxidation step, and
wherein each optionally present derivative is at least one selected from the group consisting of diacid, diether, diester, ether-acid, ether-ester, ester-acid, ester-aldehyde, ether-aldehyde, ether-acetal, ester-acetal, acetal-acid, alcohol-acid, alcohol-ester, alcohol-acetal, diol, diacetal, and aldehyde-acetal.

21. An integrated process

Assignees

• Du Pont
• Archer Daniels Midland Co
• Dupont Ind Biosciences Usa Llc

Inventors

• Howard Stephen J
• Kreutzer Kristina A
• Rajagopalan Bhuma
• Sacia Eric R
• Sanborn Alexandra
• Smith Brennan

Classifications

• C08G63/80

  Solid-state polycondensation · CPC title

• C08G63/78

  Preparation processes · CPC title

• C08G63/672

  Dicarboxylic acids and dihydroxy compounds · CPC title

• B01J2231/70

  Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues · CPC title

• C08G63/181

  Acids containing aromatic rings · CPC title