Methods and compounds for producing nylon 12
Nylon 12 may be produced by dimerization of 6-carbon furan compounds into 12-carbon dimers, and conversion of the dimers into nylon 12. The 6-carbon furan compounds may be produced from biomass. Ester-aldehyde dimers and amino-ester dimers may be produced from the 6-carbon furan compounds as precursors for at least the production of nylon 12, and the components for producing the nylon 12 may be provided as a kit.
1. A method to produce nylon 12, the method comprising:
converting alkyl furan compounds of formula
to an ester-aldehyde dimer of formula
wherein X is —OH or halogen, R is C 1 -C 5 alkyl, and M1 is
converting the ester-aldehyde dimer to an amino-ester of formula
and
converting the amino-ester to nylon 12.
2. The method of claim 1 , wherein converting the amino-ester to nylon 12 comprises treating the amino-ester with a halide source and hydrogen gas in a presence of a catalyst.
3. The method of claim 2 , wherein converting the amino-ester to nylon 12 comprises a single pot reaction wherein:
amino-esters having M1 of
produce intermediary products of
and amino-esters having M1 of
produce intermediary products of
where n≥2.
4. The method of claim 2 , wherein treating the amino-ester comprises treating with hydrogen iodide, hydrogen chloride, hydrogen bromide, or any combination thereof in a presence of a catalyst including platinum, palladium, rhodium, ruthenium, nickel, cobalt, iron, molybdenum, iridium, rhenium, gold, or any combination thereof.
5. The method of claim 1 , wherein converting the alkyl furan compounds comprises converting alkyl furan compounds including 5-chloromethyl furan compounds and 5-hydroxymethyl furan compounds; and
converting the alkyl furan compounds to the ester-aldehyde dimer comprises:
converting the 5-chloromethyl furan compounds to a dimethylacetal protected Wittig reagent of formula
oxidizing the 5-hydroxymethyl furan compounds to produce a carboxylic acid
and alkylating the carboxylic acid to produce a carboxylic acid alkyl ester of formula
and reacting the Wittig reagent with the carboxylic acid alkyl ester to produce the ester-aldehyde dimer.
6. The method of claim 5 , wherein converting the 5-chloromethyl furan compounds to the dimethylacetal protected Wittig reagent comprises treating the 5-chloromethyl furan compounds with triphenylphosphine, triarylphosphine, trialkyphosphine, diarylalkylphosphine, or any combination thereof, followed by contacting with an alcohol in a presence of an acid catalyst.
7. The method of claim 5 , wherein oxidizing the 5-hydroxymethyl furan compounds comprises oxidizing the 5-hydroxymethyl furan compounds under phase transfer conditions with 4-benzoyloxy-2,2,6,6-tetramethylpiperidin-1-oxyl.
8. The method of claim 1 , wherein converting the ester-aldehyde dimer to the amino-ester comprises aminating the ester-aldehyde dimer with at least one of ammonium hydroxide, ammonia, and hydroxylamine in a presence of hydrogen and a catalyst.
9. The method of claim 1 , wherein converting the ester-aldehyde dimer to the amino-ester comprises:
treating the ester-aldehyde dimer with hydroxylamine to produce a corresponding ester-oxime; and
treating the ester-oxime with hydrogen and a nickel catalyst to produce the amino-ester.
10. The method of claim 1 , wherein converting the ester-aldehyde dimer to the amino-ester comprises treating the ester-aldehyde dimer with a mixture of sodium cyanoborohydride, ammonium acetate, aqueous ammonium hydroxide, and an alcohol.
11. The method of claim 1 , wherein converting the alkyl furan compounds comprises converting alkyl furan compounds where M1 is
and R is methyl; converting the alkyl furan compounds to the ester-aldehyde dimer comprises:
converting 5-chloromethylfurfural to a dimethylacetal protected Wittig reagent of formula
oxidizing 5-hydroxymethylfurfural to 5-formylfuroic acid, and methylating the 5-formylfuroic acid to produce methyl 5-formylfuroate of formula
and
reacting the Wittig reagent with the methyl 5-formylfuroate to produce an ester-aldehyde dimer of formula
converting the ester-aldehyde dimer to the amino-ester comprises amination of the ester-aldehyde dimer of formula
to produce an amino-ester of formula
and
converting the amino-ester to nylon 12 comprises a single-pot hydrogenation-hydrodeoxygenation-polymerization reaction via intermediary products of
where n≥2.
12. The method of claim 1 , wherein waste biomass is used to obtain the alkyl furan compounds.
13. The method of claim 12 , wherein:
a first portion of the biomass is converted to 5-chloromethylfurfural;
a second portion of the biomass is converted to 5-hydroxymethylfurfural; and
wherein the 5-chloromethylfurfural and 5-hydroxymethylfurfural are converted to nylon 12.
14. The method of claim 13 , wherein converting the second portion of the biomass to 5-hydroxymethylfurfural comprises heating biomass derived hexoses, cellulose, or combination thereof in a presence of at least one of an acid and a metal salt catalyst to produce the 5-hydroxymethylfurfural.
15. The method of claim 13 , wherein converting the first portion of the biomass to 5-chloromethylfurfural comprises heating biomass derived hexoses, sucrose, cellulose, corn stover, or combination thereof in a presence of at least one of 1,2-dichloroethane, an alkaline salt and an acid to produce the 5-chloromethyl furfural.
16. The method of claim 13 , wherein converting the 5-chloromethylfurfural and 5-hydroxymethylfurfural to nylon 12 comprises:
producing an intermediary ester-aldehyde dimer of formula
from the 5-chloromethylfurfural and 5-hydroxymethylfurfural, wherein R is C1-C5 alkyl;
converting the ester-aldehyde dimer to an amino-ester of formula
and
converting the amino-ester to nylon 12.
17. The method of claim 16 , wherein converting the amino-ester to nylon 12 comprises treating the amino-ester with a halide source and hydrogen gas in a presence of a catalyst.
18. The method of claim 17 , wherein converting the amino-ester to nylon 12 comprises a single pot reaction with intermediary products of
wherein n≥2.
19. The method of claim 17 , wherein converting the amino-ester to nylon 12 comprises treating with hydrogen iodide, hydrogen chloride, hydrogen bromide, or a combination thereof and a catalyst comprising platinum, palladium, rhodium, ruthenium, nickel, cobalt, iron, molybdenum, iridium, rhenium, gold, or any combination thereof.
20. The method of claim 16 , wherein producing the intermediary ester-aldehyde dimer comprises:
converting 5-chloromethylfurfural to a dimethylacetal protected Wittig reagent of formula
oxidizing 5-hydroxymethylfurfural to produce a carboxylic acid of formula
and alkylating the carboxylic acid to produce a carboxylic acid alkyl ester of formula
and
reacting the Wittig reagent with the carboxylic acid alkyl ester to produce the ester-aldehyde dimer.
21. The method of claim 20 , wherein converting 5-chloromethylfurfural to the dimethylacetal protected Wittig reagent comprises treating the 5-chloromethyl furan with triphenylphosphine, triarylphosphine, trialkyphosphine, diarylalkylphosphine, or any combination thereof, followed by reaction with an alcohol in the presence of an acid catalyst.
22. The method of claim 20 , wherein oxidizing the 5-hydroxymethylfurfural comprises oxidizing the 5-hydroxymethylfurfural with 4-benzoyloxy-2,2,6,6-tetramethylpiperidin-1-oxyl under a phase transfer condition.
23. The method of claim 16 , wherein converting the ester-aldehyde dimer to the amino-ester comprises:
treating the ester-aldehyde dimer with hydroxylamine to produce a corresponding ester-oxime; and
treating the ester-oxime with hydrogen and a nickel catalyst to produce the amino-ester.
24. The method of claim 1 , wherein the converting alkyl furan compounds to the ester-aldehyde dimer comprises:
converting a first alkyl furan compound having X=halogen to a dimethylacetal protected Wittig reagent of formula
oxidizing a second alkyl furan compound having X═OH to produce a carboxylic acid of formula
alkylating the carboxylic acid to produce a carboxylic acid alkyl ester of formula
and
reacting the Wittig reagent with the carboxylic acid alkyl ester to produce the ester-aldehyde dimer.
25. The method of claim 24 , wherein converting the first alkyl furan compound comprises converting 5-chloromethylfurfural and oxidizing the second alkyl furan compound comprises oxidizing 5-hydroxymethylfurfural.
26. The method of claim 24 , wherein oxidizing the second alkyl furan compound comprises oxidizing 5-hydroxymethylfurfural to produce 5-formylfuroic acid and alkylating the carboxylic acid comprises methylating the 5-formylfuroic acid to produce methyl 5-formylfuroate of formula
27. The method of claim 26 , wherein reacting the Wittig reagent with the carboxylic acid alkyl ester comprises reacting the Wittig reagent with the methyl 5-formylfuroate to produce an ester-aldehyde dimer of formula
28. The method of claim 24 , wherein converting the ester-aldehyde dimer to the amino-ester comprises aminating an ester-aldehyde dimer of formula
to produce an amino-ester of formula