Oxygenated aromatic amines and use as antioxidants

Patent metadata

Field	Value
Publication number	US-12312291-B2
Application number	US-202016860922-A
Country	US
Kind code	B2
Filing date	Apr 28, 2020
Priority date	Apr 29, 2019
Publication date	May 27, 2025
Grant date	May 27, 2025

Abstract

Described are compounds, compositions, and methods that include oxygenated aromatic amines, such as an aminophenol-, phenyl-p-phenylenediamine-, and diaminobenzene-based compound useful as antioxidants. The oxygenated aromatic amine includes a secondary and/or tertiary amine group having a nitrogen that is attached to one or two carbon-containing group(s), the carbon-containing group(s) having a hydroxyl and/or ether group separated from the nitrogen by one or more carbon atoms.

First claim

What is claimed is:

1. A method for inhibiting oxidation of an organic compound, the method comprising:
(1a) adding a compound of Formula Ia to a composition comprising an organic compound, the compound of Formula Ia being:

wherein —R 1 , —R 2 , —R 3 , —R 4 , and —R 5 are independently selected from —H, —OH, alkyl, aryl, alkyl aryl, and aryl alkyl, or any two adjacent groups of —R 1 , —R 2 , —R 3 , —R 4 , and —R 5 form one or more ring structures;
wherein both of R 6 and R 7 are of the formula: —(CR 10 2 ) q (CHOH) (CH 2 ) z R 11 , wherein R 10 is independently selected from —H and alkyl, q and z are independently 0 (a covalent bond) or an integer in the range of 1-12, and R 11 is selected from the group consisting of C1-C24 linear, branched, or cyclic alkyl, aryl, alkyl-aryl, and aryl-alkyl; or
wherein one or both of R 6 and R 7 are of the formula: —(CR 10 2 ) q (CHOH)(R 12 O) z R 11 , wherein R 10 is independently selected from —H and alkyl, q is 0 (a covalent bond) or an integer in the range of 1-12, R 11 is selected from the group consisting of C1-C24 linear, branched, or cyclic alkyl, aryl, alkyl-aryl, and aryl-alkyl, and R 12 is independently selected from —(CH 2 ) w —, wherein w is 1, 2, or 3, and z is an integer in the range of 1-5; and one of R 6 and R 7 is optionally —H, alkyl, aryl, alkyl-aryl, aryl-alkyl, or a carbon-containing group including one or more hydroxyl group(s) separated from the N atom by one or more carbon atoms; or
(1b) adding a compound of Formula Ib to a composition comprising an organic compound, the compound of Formula Ib being:

wherein —R 1 , —R 2 , —R 3 , —R 4 , and —R 5 are independently selected from —H, OH, alkyl, aryl, alkyl aryl and aryl alkyl, and —NR 8 R 9 , wherein R 8 and R 9 are independently selected from —H, alkyl, aryl, alkyl aryl and aryl alkyl, and R 6 /R 7 as described herein, or any two adjacent groups of —R 1 , —R 2 , —R 3 , —R 4 , and —R 5 form one or more ring structures;
wherein one or both of R 6 and R 7 include at least two oxygens, at least one oxygen in the form of an ether group, and at least one oxygen in the form of a hydroxyl group, wherein the one or more hydroxyl group(s) are separated from the N atom by one or more carbon atoms, wherein one or both of R 6 and R 7 are of the formula —(CR 10 2 ) q (CHOH)(R 12 O) z R 11 , wherein R 10 is independently selected from —H and alkyl, q is 0 (a covalent bond) or an integer in the range of 1-12, R 11 is selected from the group consisting of C1-C24 linear, branched, or cyclic alkyl, aryl, alkyl-aryl, and aryl-alkyl, and R 12 is independently selected from —(CH 2 ) w —, wherein w is 1, 2, or 3, and z is an integer in the range of 1-5;
wherein the compound of Formula Ia or Formula Ib inhibits oxidation of the organic compound in the composition, and wherein
(I) the organic compound is present in a lubricant composition,
(II) the organic compound is present in a fuel composition that is a gasoline or a gasoline blend comprises pyrolysis gasoline, a refined product of pyrolysis gasoline, ethanol, or a combination thereof, or
(III) the organic compound is present in (a) a rubber composition, a plastic composition, or an adhesive composition, or (b) a food or beverage composition.

2. The method of claim 1 wherein the organic compound comprises an ethylenically unsaturated group, the organic compound being an olefin or alkene.

3. The method of claim 1 wherein the organic compound is present in (I) or (II).

4. The method of claim 1 wherein the compound of Formula Ia or Formula Ib is present in the composition in an amount in the range of 1 ppm to 5000 ppm.

5. The method of claim 4 wherein the compound of Formula Ia or Formula Ib is present in the composition in an amount in the range of 10 ppm to 2500 ppm, or optionally in an amount in the range of 50 ppm to 1500 ppm.

6. The method of claim 1 , wherein at least one of —R 1 , —R 2 , —R 3 , —R 4 , and —R 5 is —OH.

7. The method of claim 1 , wherein Formula Ia or Formula Ib, the one or more hydroxyl group(s) are separated from the N atom by two or more carbon atoms.

8. The method of claim 7 , wherein the one or more hydroxyl group(s) are separated from the N atom by two carbon atoms.

9. The method of claim 6 , wherein —R 1 , —R 2 , —R 3 , —R 4 , and —R 5 that is or are not —OH are —H.

10. The method of claim 1 wherein Formula Ia both of R 6 and R 7 are of the formula: —(CR 10 2 ) q (CHOH)(CH 2 ) z R 11 .

11. The method of claim 10 wherein the compound is selected from the group consisting of: 4-bis[(2-hydroxyethyl)amino]phenol, 4-bis[(2-hydroxypropyl)amino]phenol, 4-bis[(2-hydroxybutyl)amino]phenol, 4-bis[(2-hydroxypentyl)amino]phenol, 4-bis[(2-hydroxyhexyl)amino]phenol, 4-bis[(2-hydroxy-2-phenyl)amino]phenol, 4-bis[(2-hydroxy-2-phenylethyl)amino]phenol, 4-bis[(2-hydroxyheptyl)amino]phenol, 4-bis[(2-hydroxyoctyl)amino]phenol, 4-bis[(2-hydroxynonyl)amino]phenol,4-bis[(2-hydroxydecyl)amino]phenol, 4-bis[(2-hydroxyundecyl)amino]phenol, 4-bis[(2-hydroxydodecyl)amino]phenol, 4-bis[(2-hydroxytridecyl)amino]phenol, 4-bis[(2-hydroxytetradecyl)amino]phenol, 4-bis[(2-hydroxypentadecyl)amino]phenol, 4-bis[(2-hydroxyhexadecyl)amino]phenol, 4-bis[(2-hydroxyheptadecyl)amino]phenol, 4-bis[(2-hydroxyoctadecyl)amino]phenol, 4-bis[(2-hydroxyeleyl)amino]phenol, 4-bis[(2-hydroxynonadecyl)amino]phenol, 4-bis[(2-hydroxyeicosyl)amino]phenol, 4-bis[(2-hydroxyheneicosyl)amino]phenol, 4-bis[(2-hydroxydocosyl)amino]phenol, and 4-bis[(2-hydroxytricosyl)amino]phenol.

12. The method of claim 1 , wherein Formula Ia, both of R 6 and R 7 are of the formula: —(CR 10 2 ) q (CHOH)(R 12 O) z R 11 .

13. The method of claim 12 , wherein q is 0 (a covalent bond), 1, or 2.

14. The method of claim 1 , wherein Formula Ia R 10 is —H, q is 1; s is 1; w is 1 or 2, and R 11 is C1-C18 linear, branched, or cyclic alkyl, aryl, alkyl-aryl, and aryl-alkyl.

15. The method of claim 14 , wherein the compound is selected from the group consisting of 4-bis[(3-methoxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-ethoxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-propoxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-butoxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-pentyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-hexyloxy-2-hydroxy propyl)amino]phenol, 4-bis[(3-heptyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-octyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-nonyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-decyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-undecyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-dodecyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-tridecyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-tetradecyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-pentadecyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-hexadecyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-heptadecyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-octadecyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-eleyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-nonadecyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-eicosyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-heneicosyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-docosyloxy-2-hydroxy-propyl)amino]phenol, and 4-bis[(3-tricosyloxy-2-hydroxy propyl)amino]phenol.

16. The method of claim 1 , wherein Formula Ib at least one of —R 1 , —R 2 , —R 3 , —R 4 , and —R 5 is NR 8 R 9 .

17. T

Assignees

• Ecolab Usa Inc

Inventors

• Dhawan Ashish
• Syed Abuzar
• Pennington Janelle

Classifications

• C10L2230/081

  Anti-oxidants · CPC title

• C10L1/2235

  hydroxy containing (C10L1/221, C10L1/2227 take precedence) · CPC title

• C07C213/08

  by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups · CPC title

• C10N2040/25

  Internal-combustion engines · CPC title

• C10N2030/12

  Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives · CPC title