Humic acid derivatives and methods of preparation and use

Patent metadata

Field	Value
Publication number	US-9556134-B2
Application number	US-201314894660-A
Country	US
Kind code	B2
Filing date	May 28, 2013
Priority date	May 28, 2013
Publication date	Jan 31, 2017
Grant date	Jan 31, 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 a compound of formula V:

wherein
R 11 is —N(R 111 )(R 112 ), wherein R 111 is C-acetamido or substituted C-acetamido; R 112 is hydrogen, —(C 1 -C 20 )alkyl, substituted —(C 1 -C 20 )alkyl, —(C═O)—(C 3 -C 19 )alkyl, or substituted -(C═O)—(C 3 -C 19 )alkyl;
R 12 , R 141 , R 142 , R 143 , and R 144 are independently hydrogen, —(C 1 -C 20 )alkyl, or substituted —(C 1 -C 20 )alkyl;
R 13 is hydrogen, —(C 1 -C 20 )alkyl, substituted —(C 1 -C 20 )alkyl, —(C═O)—(C 3 -C 19 )alkyl, or substituted —(C═O)—(C 3 -C 19 )alkyl;
R 16 is a hydrogen, glucuronate or substituted glucuronate;
R 151 , R 152 , R 153 , R 154 , R 155 , and R 156 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 141 , R 142 , R 143 , R 144 , R 151 , R 152 , R 153 , R 154 , R 155 , and R 156 is not hydrogen;
a salt, chelate, or combination thereof.

2. The compound of claim 1 , wherein the compound is a salt thereof.

3. The compound of claim 1 , wherein R 141 , R 142 , R 143 , and R 144 are independently hydrogen or —(C 4 -C 20 )alkyl.

4. The compound of claim 1 , wherein R 151 , R 152 , R 153 , R 154 , R 155 , and R 156 are independently hydrogen or —(C═O)—(C 3 -C 19 )alkyl.

5. The compound of claim 1 , wherein the compound is a lithium salt, sodium salt, ammonium salt, potassium salt, calcium salt, barium salt, magnesium salt, manganese salt, zinc salt, aluminum salt, iron salt, or a combination thereof.

6. The compound of claim 1 , wherein the compound is a polyvalent cation chelate.

7. The compound of claim 1 , wherein the compound is a calcium chelate, magnesium chelate, iron chelate, or zinc chelate or combination thereof.

8. 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 V a salt or chelate thereof:

wherein:
R 11 is —N(R 111 )(R 112 ), wherein R 111 is C-acetamido or substituted C-acetamido;
R 112 is hydrogen, —(C 1 -C 20 )alkyl, substituted —(C 1 —C 20 )alkyl, —(C═O)—(C 3 -C 19 alkyl, or substituted —(C═O)—(C 3 -C 19 )alkyl;
R 12 , R 141 , R 142 , R 143 and R 144 are independently hydrogen, -(C 4 —C 20 )alkyl, or substituted —(C 4 -C 20 alkyl;
R 13 is hydrogen, —(C 1 -C 20 alkyl, substituted —(C 1 -C 20 )alkyl, —(C═O)—(C 3 —C 19 )alkyl, or substituted —(C═O)—(C 3 -C 19 )alkyl;
R 16 is hydrogen, glucuronate, or substituted glucuronate;
R 151 , R 152 , R 153 , R 154 , R 155 , and R 156 are independently hydrogen, —(C═O)—(C 3 -C 19 )alkyl, or substituted —(C═O)—(C 3 -C 19 )alkyl;
R 141 , R 142 , R 143 , R 144 , R 151 , R 152 , R 153 , R 154 , R 155 , and R 156 are hydrogen; and
esterifying at least one functional group of the mixture of compounds to give a polymer stabilizing mixture of compounds.

9. The method of claim 8 , further comprising forming a chelate of the compound of the polymer stabilizing mixture with a calcium cation, magnesium cation, zinc cation, iron cation, or combinations thereof.

10. The method of claim 8 , further comprising forming a salt of the compound of the polymer stabilizing mixture to form a lithium salt, sodium salt, ammonium salt, potassium salt, calcium salt, barium salt, magnesium salt, manganese salt, zinc salt, aluminum salt, iron salt, or a combination thereof.

11. The method of claim 8 , further comprising purifying the compound of the polymer stabilizing mixture.

12. The method of claim 8 , further comprising isolating the compound of formula V wherein at least one of R 141 , R 142 , R 143 , R 144 , R 151 , R 152 , R 153 , R 154 , R 155 , and R 156 is not hydrogen; 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.

13. The method of claim 8 , wherein the humic acid comprises at least one compound of formula I:

salt, or chelate thereof, wherein
R 11 is —N(R 111 )(R 112 ), wherein R 111 is C-acetamido or substituted C-acetamido; R 112 is hydrogen, —(C 1 —C 20 )alkyl, substituted —(C 1 -C 20 )alkyl, —(C═O)—(C 3 -C 19 )alkyl, or substituted —(C═O)—(C 3 —C 19 )alkyl;
R 12 is hydrogen, —(C 1 -C 20 )alkyl, or substituted —(C 1 -C 20 )alkyl;
R 13 is hydrogen, —(C 1 -C 20 )alkyl, substituted —(C 1 -C 20 )alkyl, —(C═O)—(C 3 -C 19 )alkyl, or substituted —(C═O)—(C 3 -C 19 )alkyl; and
R 16 is a hydrogen, glucuronate or substituted glucuronate.

14. The method of claim 8 , wherein the hydrolyzing comprises hydrolyzing in the presence of an alkaline solution.

15. The method of claim 14 , wherein the alkaline solution is aqueous lithium hydroxide, aqueous sodium hydroxide, aqueous potassium hydroxide, or combination thereof.

16. The method of claim 8 , wherein the hydrolyzing comprises hydrolyzing at a pH of 8.5-13.

Assignees

• Empire Technology Dev Llc

Inventors

• Adam Georgius Abidal
• Needham Anita

Classifications

• C09K15/30

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

• C09K15/06

  containing oxygen · CPC title

• C08K5/357

  Six-membered rings · CPC title

• C08K5/1535

  Five-membered rings · CPC title

• C07D307/77

  ortho- or peri-condensed with carbocyclic rings or ring systems · CPC title