Humic acid derivatives and methods of preparation and use

Patent metadata

Field	Value
Publication number	US-2017088528-A1
Application number	US-201615377666-A
Country	US
Kind code	A1
Filing date	Dec 13, 2016
Priority date	May 28, 2013
Publication date	Mar 30, 2017
Grant date	—

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

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 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 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
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, chelate, or combination thereof.

2 . The compound of claim 1 , wherein the humic acid derivative of formula VI, formula VII, formula VIII, a salt, chelate, or 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 .- 6 . (canceled)

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

8 .- 9 . (canceled)

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

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

12 . 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.

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

14 .- 16 . (canceled)

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

18 - 22 . (canceled)

23 . 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, ab aluminum salt, and an iron salt, or a combination thereof.

24 . (canceled)

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

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

27 . 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, chelate or 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 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 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 , R23, R24, 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.

28 . (canceled)

29 . The method of claim 27 , wherein esterifying comprises forming a —(C═O)—(C3-C19)alkyl ester of at least one of R23, R24, R25, R26, R27, R33, R34, R35, R36, R42, R43, and R44, to give an esterified mixture.

30 . The method of any one of claims 27 , wherein esterifying comprises forming a —(C4-C20)alkyl ester of at least one of R21, R22, R31, R32, and R41, to give an esterified mixture.

31 . (canceled)

32 . The method of claim 27 , further comprising forming a chelate of at least one compound of the polymer stabilizing mixture with a calcium cation, magnesium cation, zinc cation, iron cation, or combinations thereof.

33 . (canceled)

34 . The method of claim 27 , further comprising forming a salt of at least one 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.

35 . The method of claim 27 , further comprising purifying at least one compound of the polymer stabilizing mixture.

36 .- 37 . (canceled)

38 . The method of claim 27 , 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.

39 . The method of claim 27 , 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.

40 . The method of claim 27 , 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.

41 . The method of claim 27 , 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.

42 . The

Assignees

• Empire Technology Dev Llc

Inventors

• Adam Georgius Abidal
• Needham Anita

Classifications

• C08K5/357

  Six-membered rings · CPC title

• C07D265/38 Primary

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

• C09K15/06

  containing oxygen · CPC title

• C07D413/14

  containing three or more hetero rings · CPC title

• C08K5/1535

  Five-membered rings · CPC title