Humic acid derivatives and methods of preparation and use

Patent metadata

Field	Value
Publication number	US-9840480-B2
Application number	US-201615377666-A
Country	US
Kind code	B2
Filing date	Dec 13, 2016
Priority date	May 28, 2013
Publication date	Dec 12, 2017
Grant date	Dec 12, 2017

Abstract

Disclosed are antioxidative natural compounds, their salts, chelates and cleavage derivatives that exhibit a superior combination of properties. The compounds can be used for a variety of purposes, including the stabilization of polymers. The compounds can be prepared by substantially cleaving a humic acid of formula I followed by esterification to provide at least one antioxidant compounds of formula V, formula VI, formula VII, formula VIII, salts thereof, or chelates thereof.

First claim

What is claimed is:

1. A stabilizing compound comprising at least one humic acid derivative, wherein the humic acid derivative is selected from the group consisting of formula VI, formula VII, and formula VIII:

R 2 is hydrogen, —(C 1 -C 20 )alkyl, or substituted —(C 1 -C 20 )alkyl;
R 4 is hydrogen, —(C 1 -C 20 )alkyl, or substituted —(C 1 -C 20 )alkyl;
R 21 , R 22 , R 31 , R 32 , and R 41 are independently hydrogen, —(C 4 -C 20 )alkyl, or substituted —(C 4 -C 20 )alkyl;
R 23 , R 24 , R 25 , R 26 , R 27 , R 33 , R 34 , R 35 , R 36 , R 42 , R 43 , and R 44 are independently hydrogen, —(C═O)—(C 3 -C 19 )alkyl, or substituted —(C═O)—(C 3 -C 19 )alkyl; and
wherein at least one of R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 is not hydrogen; at least one of R 31 , R 32 , R 33 , R 34 , R 35 , and R 36 is not hydrogen; and at least one of R 41 , R 42 , R 43 , and R 44 is not hydrogen;
a salt, a chelate, or a combination thereof.

2. The compound of claim 1 , wherein the humic acid derivative of formula VI, formula VII, formula VIII, a salt, a chelate, or a combination thereof comprises:
R 2 is hydrogen or —(C 1 -C 20 )alkyl;
R 23 , R 24 , R 25 , R 26 , and R 27 , are independently hydrogen or —(C═O)—(C 3 -C 19 )alkyl;
R 4 is hydrogen or —(C 1 -C 20 )alkyl;
R 41 is independently hydrogen or —(C 4 -C 20 )alkyl; and
R 42 , R 43 , and R 44 are independently hydrogen or —(C═O)—(C 3 -C 19 )alkyl, wherein at least one of R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 41 , R 42 , R 43 , and R 44 is not hydrogen.

3. The compound of claim 1 , wherein the humic acid derivative comprises formula VI, a salt thereof, or a chelate thereof.

4. The compound of claim 1 , wherein R 2 is methyl.

5. The compound of claim 1 , wherein R 21 R 22 , are independently hydrogen or —(C 4 -C 20 )alkyl.

6. The compound of claim 1 , wherein R 23 , R 24 , R 25 , R 26 , and R 27 , are independently hydrogen or —(C═O)—(C 3 -C 19 )alkyl; and wherein at least one of R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 is not hydrogen.

7. The compound of claim 1 , wherein the humic acid derivative is formula VII, a salt thereof, or a chelate thereof.

8. The compound of claim 1 , wherein the humic acid derivative is formula VIII, a salt thereof, or a chelate thereof.

9. The compound of claim 1 , wherein the salt is selected from the group consisting of a lithium salt, a sodium salt, an ammonium salt, a potassium salt, a calcium salt, a barium salt, a magnesium salt, a manganese salt, a zinc salt, an aluminum salt, and an iron salt.

10. The compound of claim 1 , wherein the humic acid derivative is a polyvalent cation chelate.

11. The compounds of claim 1 , wherein the humic acid derivative is independently a calcium chelate, a magnesium chelate, an iron chelate, a zinc chelate or a combination thereof.

12. A method of preparing a polymer stabilizing mixture of compounds, the method comprising:
substantially hydrolyzing a humic acid to form a mixture of compounds according to formula VI, formula VII and formula VIII, a salt, a chelate, or a combination thereof:

wherein:
R 2 is hydrogen, —(C 1 -C 20 )alkyl, or substituted —(C 1 -C 20 )alkyl;
R 4 is hydrogen, —(C 1 -C 20 )alkyl, or substituted —(C 1 -C 20 )alkyl;
R 21 , R 22 , R 31 , R 32 , and R 41 are independently hydrogen, —(C 4 -C 20 )alkyl, or substituted —(C 4 -C 20 )alkyl;
R 23 , R 24 , R 25 , R 26 , R 27 , R 33 , R 34 , R 35 , R 36 , R 42 , R 43 , and R 44 are independently hydrogen, —(C═O)—(C 3 -C 19 )alkyl, or substituted —(C═O)—(C 3 -C 19 )alkyl;
wherein at least one of R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 is not hydrogen; at least one of R 31 , R 32 , R 33 , R 34 , R 35 , and R 36 is not hydrogen; and at least one of R 41 , R 42 , R 43 , and R 44 is not hydrogen; and
esterifying at least one functional group of the mixture of compounds to give a polymer stabilizing mixture of compounds.

13. The method of claim 12 , wherein esterifying comprises forming a alkyl ester of at least one of R 23 , R 24 , R 25 , R 26 , R 27 , R 33 , R 34 , R 35 , R 36 , R 42 , R 43 , and R 44 , to give an esterified mixture.

14. The method of claim 12 , wherein esterifying comprises forming a (C 4 -C 20 )alkyl ester of at least one of R 21 , R 22 , R 31 , R 32 , and R 41 , to give an esterified mixture.

15. The method of claim 12 , further comprising forming a chelate of at least one compound of the polymer stabilizing mixture with a calcium cation, a magnesium cation, a zinc cation, an iron cation, or a combination thereof.

16. The method of claim 12 , further comprising forming a salt of at least one compound of the polymer stabilizing mixture to form a lithium salt, a sodium salt, an ammonium salt, a potassium salt, a calcium salt, a barium salt, a magnesium salt, a manganese salt, a zinc salt, an aluminum salt, an iron salt, or a combination thereof.

17. The method of claim 12 , further comprising purifying at least one compound of the polymer stabilizing mixture.

18. The method of claim 12 , further comprising isolating a compound of the polymer stabilizing mixture of formula VI, wherein at least one of R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 is not hydrogen.

19. The method of claim 12 , further comprising isolating a compound of the polymer stabilizing mixture of formula VII, wherein at least one of R 31 , R 32 , R 33 , R 34 , R 35 , and R 36 is not hydrogen.

20. The method of claim 12 , further comprising isolating a compound of the polymer stabilizing mixture of formula VIII, wherein at least one of R 41 , R 42 , R 43 , and R 44 is not hydrogen.

21. The method of claim 12 , wherein the hydrolyzing comprises hydrolyzing in the presence of an alkaline solution.

22. The method of claim 21 , wherein the alkaline solution is aqueous lithium hydroxide, aqueous sodium hydroxide, aqueous potassium hydroxide, or a combination thereof.

23. The method of claim 12 , wherein the hydrolyzing comprises hydrolyzing at a pH of 8.5-13.

Assignees

• Empire Technology Dev Llc

Inventors

• Adam Georgius Abidal
• Needham Anita

Classifications

• C08K5/1535

  Five-membered rings · CPC title

• C07D265/38 Primary

  [b, e]-condensed with two six-membered rings · CPC title

• C08K5/357

  Six-membered rings · CPC title

• C09K15/30

  containing heterocyclic ring with at least one nitrogen atom as ring member · CPC title

• C09K15/06

  containing oxygen · CPC title