Substituted benzotriazole phenolate salts and antioxidant compositions formed therefrom

Patent metadata

Field	Value
Publication number	US-10669481-B2
Application number	US-201615741680-A
Country	US
Kind code	B2
Filing date	Jun 30, 2016
Priority date	Jul 7, 2015
Publication date	Jun 2, 2020
Grant date	Jun 2, 2020

Abstract

A class of antioxidant compositions include benzotriazole phenolate salts with substituents either ortho to the phenol hydroxide group and/or para to the phenol hydroxide group can be prepared from substituted benzotriazole phenols. The ortho substituent group can be a simple hydrocarbon, alkoxy or amino group, or the ortho substituent group can be a linking group, linking the benzotriazole phenolate to another benzotriazole phenolate group.

First claim

What is claimed is:

1. An antioxidant composition comprising one or more macromolecular salt compositions, the macromolecular salt composition comprising an assembly of metal salts comprising repeat units of a substituted benzotriazole phenolate anion and a metal cation with the structure:

wherein each R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 , independently comprises a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a halogen atom, or a substituted heteroatom group comprising a —B(OR 18 )(OR 19 ), a —SiR 20 3 , a —CH 2 —R 9 , an —O—R 9 , a —N—R 9 R 10 , a —S—R 9 ,
a —S(O)—R 9 , or a —S(O) 2 —R 9 group, wherein R 9 comprises a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heteroatom-containing group comprising one or more oxygen, nitrogen, sulfur, or phosphorous atoms, wherein the —B(OR 18 )(OR 19 ), —SiR 20 3 ,
—CH 2 —R 9 , —O—R 9 , —N—R 9 R 10 , —S—R 9 , —S(O)—R 9 , or —S(O) 2 —R 9 group may be neutral or anionic, and R 10 comprises a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heteroatom-containing group comprising one or more oxygen, nitrogen, sulfur, or phosphorous atoms, or R 9 and R 10 together with the atoms connecting form a heterocyclic ring structure, R 18 and R 19 are independently hydrogen atoms, alkyl groups or R 18 and R 19 together with the atoms connecting form a heterocyclic ring structure, each R 20 independently comprises an alkyl group; R 1 is a hydrogen atom, a substituted alkyl group, an alkenyl group, an aryl group, a halogen atom, or a substituted heteroatom group comprising a —B(OR 8 )(OR 19 ), a —SiR 20 3 , a —CH 2 —R 9 , an —O—R 9 , a —N—R 9 R 10 , a —S—R 9 , a —S(O)—R 9 , or a —S(O) 2 —R 9 group, and wherein when R 1 is hydrogen, R 3 is an alkyl group comprising 4 carbon atoms, or an alkoxy group;
n=1; and
M comprises a metal atom with a valency of n; and
the macromolecular assembly comprises 2-4 repeat units.

2. The antioxidant composition of claim 1 , wherein M comprises lithium, sodium, or potassium.

3. The antioxidant composition of claim 1 , wherein R 1 comprises an —O—R 9 group wherein R 9 comprises:
an alkyl group with 1-20 carbon atoms; or
an aryl group; and
R 3 is an alkyl group with 1-20 carbon atoms.

4. The antioxidant composition of claim 3 , wherein R 9 comprises:
an alkyl group with 1-6 carbon atoms; or
an aryl group comprising a 3-methyl phenyl group, or a 4-methyl phenyl group.

5. The antioxidant composition of claim 1 , wherein R 1 comprises an —N—R 9 R 10 group wherein R 9 comprises:
an alkyl group with 1-20 carbon atoms; or
an aryl group;
R 10 comprises a hydrogen atom or alkyl group with 1-6 carbon atoms; and

R 3 is an alkyl group with 1-20 carbon atoms.

6. The antioxidant composition of claim 5 , wherein R 9 comprises:
an alkyl group with 1-6 carbon atoms; or
an aryl group comprising a 4-alkyl substituted phenyl group, wherein the alkyl substituted group has 1-6 carbon atoms;
R 10 comprises a hydrogen atom.

7. The antioxidant composition of claim 1 , wherein R 1 comprises, a substituted alkyl, alkylene, or an aryl group; and
R 3 is an alkyl group with 1-20 carbon atoms, or an alkoxy group with 1-6 carbon atoms.

8. The antioxidant composition of claim 1 , wherein R 1 comprises a halogen atom or a —SiR 20 3 group wherein each R 20 comprises an alkyl group with 1-4 carbon atoms; and
R 3 is an alkyl group with 1-20 carbon atoms.

9. The antioxidant composition of claim 1 , wherein the antioxidant composition comprises a mixture of macromolecular salts.

10. A macromolecular salt composition comprising an assembly of metal salts comprising repeat units of a substituted benzotriazole phenolate anion and a metal cation with the structure:

wherein each R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 , independently comprises a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a halogen atom, or a substituted heteroatom group comprising a —B(OR 8 )(OR 19 ), a —SiR 20 3 , a —CH 2 —R 9 , an —O—R 9 , a —N—R 9 R 10 , a —S—R 9 ,
a —S(O)—R 9 , or a —S(O) 2 —R 9 group, wherein R 9 comprises a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heteroatom-containing group comprising one or more oxygen, nitrogen, sulfur, or phosphorous atoms, wherein the —B(OR 18 )(OR 19 ), —SiR 20 3 ,
—CH 2 —R 9 , —O—R 9 , —N—R 9 R 10 , —S—R 9 , —S(O)—R 9 , or —S(O) 2 —R 9 group may be neutral or anionic, and R 10 comprises a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heteroatom-containing group comprising one or more oxygen, nitrogen, sulfur, or phosphorous atoms, or R 9 and R 10 together with the atoms connecting form a heterocyclic ring structure, R 18 is and R 19 are independently hydrogen atoms, alkyl groups or R 18 is and R 19 together with the atoms connecting form a heterocyclic ring structure, each R 20 independently comprises an alkyl group; R 1 is a hydrogen atom, a substituted alkyl group, an alkenyl group, an aryl group, a halogen atom, or a substituted heteroatom group comprising a —B(OR 18 )(OR 19 ), a —SiR 20 3 , a —CH 2 —R 9 , an —O—R 9 , a —N—R 9 R 10 , a —S—R 9 , a —S(O)—R 9 , or a —S(O) 2 —R 9 group, and wherein when R 1 is hydrogen, R 3 is an alkyl group comprising 4 carbon atoms, or an alkoxy group;
n=1; and
M comprises a metal atom with a valency of n; and
the macromolecular assembly comprises 2-4 repeat units.

11. The salt composition of claim 10 , wherein M comprises lithium, sodium, or potassium.

12. The salt composition of claim 10 , wherein R 1 comprises an —O—R 9 group wherein R 9 comprises:
an alkyl group with 1-6 carbon atoms; or
an aryl group comprising a 3-methyl phenyl group, or a 4-methyl phenyl group; and
R 3 is an alkyl group with 1-20 carbon atoms.

13. The salt composition of claim 10 , wherein R 1 comprises an —N—R 9 R 10 group wherein R 9 comprises:
an alkyl group with 1-6 carbon atoms; or
an aryl group comprising a 4-alkyl substituted phenyl group, wherein the alkyl substituted group has 1-6 carbon atoms;
R 10 comprises a hydrogen atom or alkyl group with 1-6 carbon atoms; and

R 3 is an alkyl group with 1-20 carbon atoms.

14. The salt composition of claim 10 , wherein R 1 comprises a substituted alkyl, alkylene, or an aryl group; and
R 3 is an alkyl group with 1-20 carbon atoms, or an alkoxy group with 1-6 carbon atoms.

15. The salt composition of claim 10 , wherein R 1 comprises a halogen atom or a —SiR 20 3 group wherein each R 20 comprises an alkyl group with 1-4 carbon atoms; and
R 3 is an alkyl group with 1-20 carbon atoms.

Assignees

• 3M Innovative Properties Co

Inventors

• Schultz Nathan E
• Li Fuming B
• Volp Kelly A
• Mccormick Mark

Classifications

• C08K5/138

  Phenolates · CPC title

• C07D249/20 Primary

  with aryl radicals directly attached in position 2 · CPC title

• C09K15/24

  containing a phenol or quinone moiety · CPC title

• G01R33/46

  NMR spectroscopy · CPC title

• C08K5/0091

  Complexes with metal-heteroatom-bonds · CPC title