Methods and compounds for producing nylon 6,6

• US 9,988,491 B2
• Filed: 10/22/2013
• Issued: 06/05/2018
• Est. Priority Date: 10/22/2013
• Status: Active Grant

• Current Assignee: Empire Technology Development LLC (Allied Inventors Management, LLC)
• Original Assignee: Empire Technology Development LLC (Allied Inventors Management, LLC)
• Inventors: Klein, Josef Peter
• Primary Examiner(s): Woodward, Ana L
• Application Number:
  US15/031,687
• Publication Number:
  US 20160264733A1
• Time in Patent Office: 1,687 Days
• Field of Search: None
• CPC Class Codes: C08G 69/26 derived from polyamines and polycarboxylic acids
• CPC Class Codes: C08G 69/28 Preparatory processes
• CPC Class Codes: C08G 69/48 Polymers modified by chemical after-treatment

Abstract

Alternating co-polymers of cyclic dicarboxylic acids and cyclic diamines may be used to produce nylon 6,6. Di-substituted furan compounds may be used as the raw material for producing furan-dicarboxylic acids and/or furan-diamines. The furan-dicarboxylic acids and furan-diamines may be copolymerized to produce polymer precursors for nylon 6,6. The polymer precursors may be hydrogenated and/or deoxygenated to produce nylon 6,6.

Claims

1. A method for producing nylon 6,6, the method comprising:

converting methylfurfural of formula

2. The method of claim 1, wherein converting the polymer to nylon 6,6 comprises performing a catalytic hydrogenation reaction and catalytic hydrodeoxygenation reaction, wherein M1 and M2 are

3. The method of claim 2, wherein performing the catalytic hydrogenation reaction comprises reacting the polymer

4. The method of claim 3, wherein reacting the polymer with hydrogen comprises reacting the polymer in the presence of at least one hydrogenation catalyst including platinum, palladium, rhodium, ruthenium, nickel, cobalt, iron, molybdenum, iridium, rhenium or gold.

5. The method of claim 2, wherein the catalytic hydrodeoxygenation reaction comprises reacting the intermediate tetrahydrofuran polymer with hydrogen in the presence of at least one hydrodeoxygenation catalyst, at least one solvent, and at least one halogen source to produce the nylon 6,6 and, wherein the hydrodeoxygenation catalyst comprises platinum, palladium, rhodium, ruthenium, nickel, cobalt, iron, molybdenum, iridium, rhenium, gold, or any combination thereof, and the halogen source comprises hydrogen iodide, hydrogen bromide or a combination thereof.

6. The method of claim 1, wherein converting the methylfurfural to a furan-dicarbonyl compound comprises oxidizing 5-hydroxymethylfurfural to furan-2,5-dicarboxylic acid.

7. The method of claim 6, wherein oxidizing comprises combining 5-hydroxymethylfurfural and an oxidation catalyst in a solvent to produce a first mixture, and contacting the first mixture with an oxidant, wherein the oxidation catalyst comprises Mn(III)-salen complex, platinum, palladium, chromium (VI) oxide, pyridinium chlorochromate, bismuth (III) oxide, 2-iodoxybenzoic acid, vanadyl acetylacetonate, or any combination thereof, and the oxidant comprises sodium hypochlorite, oxygen, periodic acid, chromium (VI) oxide, pyridinium chlorochromate, hydrogen peroxide, tert-butyl hydroperoxide, potassium peroxymonosulfate, potassium permanganate, or any combination thereof.

8. The method of claim 1, wherein converting methylfurfural to furan-diamine comprises oxidizing 5-hydroxymethylfurfural to furan-2,5-dialdehyde, and performing a reductive amination of the furan-2,5-dialdehyde.

9. The method of claim 8, wherein oxidizing 5-hydroxymethylfurfural includes combining 5-hydroxymethylfurfural and an oxidant in a solvent.

10. The method of claim 9, wherein the combining comprises combining with oxygen, ceric ammonium nitrate, sodium hypochlorite, iodosobenzene diacetate, hydrogen peroxide, chromium (VI) oxide, pyridinium chlorochromate, permanganate, or any combination thereof.

11. The method of claim 9, wherein the oxidizing comprises combining 5-hydroxymethylfurfural and an oxidant in a solvent including an oxidation catalyst.

12. The method of claim 11, wherein the combining comprises combining with an oxidation catalyst including a copper (II) salt, a copper (I) salt, a cobalt (II) salt, a manganese (II) salt, ruthenium, a vanadate, iron, or any combination thereof.

13. The method of claim 8, wherein performing a reductive amination of furan-2,5-dialdehyde comprises:

combining furan-2,5-dialdehyde with ammonia or an ammonia equivalent in a solvent to form an intermediate diimine; and

treating the intermediate diimine with a reducing agent in a solvent to produce 2,5-bis(aminomethyl)furan.

14. The method of claim 13, wherein the combining furan-2,5-dialdehyde with an ammonia equivalent comprises combining with ammonium acetate, hydroxylamine, or any combination thereof;

and

the treating comprises treating with hydrogen, sodium borohydride, sodium cyanoborohydride, sodium acetoxyborohydride, or any combination thereof.

15. The method of claim 8, further comprising producing the 5-hydroxymethylfurfural from biomass.

16. The method of claim 15, wherein producing the 5-hydroxymethylfurfural from biomass comprises:

isolating hexoses from the biomass; and

dehydrating the hexoses to form the 5-hydroxymethylfurfural.

17. The method of claim 1, wherein the reacting comprises polymerizing via a polycondensation reaction.

18. The method of claim 17, wherein polymerizing via a polycondensation reaction comprises:

combining the furan-dicarbonyl compound with an activating reagent to produce an activated carboxylic acid derivative; and

combining the activated carboxylic acid derivative with the furan-diamine to produce the alternating copolymer.

19. The method of claim 18, wherein combining the furan-dicarbonyl compound comprises combining with an activating reagent including thionyl chloride or N-hydroxysuccinimide with a carbodiimide.

20. The method of claim 1, wherein converting methylfurfural comprises converting 5-hydroxymethyl furfural, and converting the methylfurfural to a furan-dicarbonyl compound comprises a catalytic oxygenation of the 5-hydroxymethyl furfural to one or more of furan-2,5-dicarboxylic acid dimethyl ester, tetrahydrofuran-2,5-dicarboxylic acid dimethyl ester.

21. The method of claim 1, wherein reacting comprises forming the polymer where n is about 5 to about 1000.