Polytriazole coating materials for metal substrates

Patent metadata

Field	Value
Publication number	US-11926758-B2
Application number	US-202117140678-A
Country	US
Kind code	B2
Filing date	Jan 4, 2021
Priority date	Jul 17, 2020
Publication date	Mar 12, 2024
Grant date	Mar 12, 2024

Abstract

Coated substrates include a metal substrate and a polytriazole polymer applied to a surface of the metal substrate. The polytriazole polymer may include substituted phenyls, substituted benzyls, or both substituted phenyls and substituted benzyls. The substituted phenyls and the substituted benzyls may be independently substituted with hydrogen, bromo, fluoro, chloro, iodo, hydroxy, methyl, trifluoromethyl, dimethylamino, tert-butyl, carboxyl, triphenylmethyl, tris(4-fluorophenyl)methyl, tris(4-methylphenyl)methyl, (4-hydroxyphenyl)diphenylmethyl, and difluoromethoxy groups. The polytriazole polymer may have a degree of polymerization from 50 to 400.

First claim

What is claimed is:

1. A coated substrate comprising a metal substrate and a polytriazole polymer on a surface of the metal substrate, the polytriazole polymer having a structure according to formula (I):

where:
R 1 and R 2 are independently selected from substituted phenyls according to formula (a) and substituted benzyls according to formula (b):

where, in formulas (a) and (b), X 1 , X 2 , X 3 , X 4 , and X 5 are independently selected from hydrogen, bromo, fluoro, chloro, iodo, hydroxy, methyl, trifluoromethyl, dimethylamino, tert-butyl, carboxyl, triphenylmethyl, tris(4-fluorophenyl)methyl, tris(4-methylphenyl)methyl, (4-hydroxyphenyl)diphenylmethyl, and difluoromethoxy, provided at least one of X 1 , X 2 , X 3 , X 4 , or X 5 is not hydrogen;

m and n represent monomer mole fractions in the polytriazole polymer;
m is from 0 to 1;
n is from 0 to 1;
m+n=1; and
the polytriazole polymer has a degree of polymerization from 50 to 400.

2. The coated substrate of claim 1 , wherein in each R 1 and each R 2 , exactly one of X 1 , X 2 , X 3 , X 4 , and X 5 is bromo, fluoro, chloro, iodo, hydroxy, methyl, trifluoromethyl, dimethylamino, tert-butyl, carboxyl, triphenylmethyl, tris(4-fluorophenyl)methyl, tris(4-methylphenyl)methyl, (4-hydroxyphenyl)diphenylmethyl, or difluoromethoxy, and the remaining four of X 1 , X 2 , X 3 , X 4 , and X 5 are hydrogen.

3. The coated substrate of claim 1 , wherein in each R 1 and each R 2 , exactly two of X 1 , X 2 , X 3 , X 4 , and X 5 are independently selected from bromo, fluoro, chloro, iodo, hydroxy, methyl, trifluoromethyl, dimethylamino, tert-butyl, carboxyl, triphenylmethyl, tris(4-fluorophenyl)methyl, tris(4-methylphenyl)methyl, (4-hydroxyphenyl)diphenylmethyl, or difluoromethoxy, and the remaining three of X 1 , X 2 , X 3 , X 4 , and X 5 are hydrogen.

4. The coated substrate of claim 1 , wherein in each R 1 and each R 2 , exactly three of X 1 , X 2 , X 3 , X 4 , and X 5 are independently selected from bromo, fluoro, chloro, iodo, hydroxy, methyl, trifluoromethyl, dimethylamino, tert-butyl, carboxyl, triphenylmethyl, tris(4-fluorophenyl)methyl, tris(4-methylphenyl)methyl, (4-hydroxyphenyl)diphenylmethyl, or difluoromethoxy, and the remaining two of X 1 , X 2 , X 3 , X 4 , and X 5 are hydrogen.

5. The coated substrate of claim 1 , wherein in each R 1 and each R 2 , X 1 , X 2 , X 3 , X 4 , and X 5 are independently selected from the group consisting of hydrogen, bromo, chloro, and fluoro, provided at least one of X 1 , X 2 , X 3 , X 4 , or X 5 is not hydrogen.

6. The coated substrate of claim 1 , wherein R 1 and R 2 are independently selected from the group consisting of
4-bromophenyl,
4-hydroxyphenyl,
4-fluorophenyl,
2,4-difluorophenyl,
2,5-difluorophenyl,
4-bromo-2,5-difluorophenyl,
4-bromo-2,6-difluorophenyl,
2-bromo-4-fluorophenyl,
2,6-dibromo-4-fluorophenyl,
3-chloro-5-fluorophenyl,
3-chloro-4-fluorophenyl,
4-fluoro-3-(trifluoromethyl)phenyl,
3-(trifluoromethyl)phenyl,
3,5-dibromo-4-methylphenyl,
3-bromo-4-methylphenyl,
2,4,6-trimethylphenyl,
4-tert-butylphenyl,
4-(dimethylamino)phenyl,
2,3,4,5,6-pentafluorophenyl,
2,4,6-trifluorobenzyl,
3,4,5-trifluorobenzyl,
4-(trifluoromethyl)benzyl,
2,3,4-trifluorobenzyl,
4-fluorobenzyl,
3,5-(di-trifluoromethyl)benzyl,
2,4,6-trimethylbenzyl,
4-methylbenzyl,
4-carboxylbenzyl,
4-(triphenylmethyl)phenyl,
4-[tris(4-fluorophenyl)methyl]phenyl,
4-[tris(4-methylphenyl)methyl]phenyl,
4-[(4-hydroxyphenyl)diphenylmethyl]phenyl,
4-(triphenylmethyl)benzyl,
4-[tris(4-fluorophenyl)methyl]benzyl,
4-[tris(4-methylphenyl)methyl]benzyl, and
4-[(4-hydroxyphenyl)diphenylmethyl]benzyl.

7. The coated substrate of claim 1 , wherein each R 1 and each R 2 are independently selected from the group consisting of
4-bromophenyl,
4-fluorophenyl,
4-hydroxyphenyl,
4-bromo-2,5-difluorophenyl,
3-(trifluoromethyl)phenyl,
2,5-difluorophenyl, and
2,3,4,5,6-pentafluorophenyl.

8. The coated substrate of claim 1 , wherein R 1 and R 2 are independently selected from the group consisting of
4-bromophenyl,
4-fluorophenyl,
4-bromo-2,5-difluorophenyl,
3-(trifluoromethyl)phenyl,
2,5-difluorophenyl, and
2,3,4,5,6-pentafluorophenyl.

9. The coated substrate of claim 1 , wherein R 1 is 4-bromophenyl and R 2 is 4-fluorophenyl.

10. The coated substrate of claim 1 , wherein the metal substrate comprises a metal or metal alloy chosen from iron, iron alloys, aluminum, aluminum alloys, copper, copper alloys, nickel, nickel alloys, lead, or lead alloys.

11. The coated substrate of claim 1 , wherein the metal substrate comprises an iron-based steel comprising at least one minor alloying component chosen from carbon, manganese, silicon, nickel, chromium, molybdenum, tungsten, niobium, vanadium, titanium, or combinations thereof.

12. The coated substrate of claim 1 , wherein m is zero and the polytriazole polymer has a structure according to formula (II):

where:
R 2 is as defined in formula (I); and
the polytriazole polymer has a degree of polymerization from 300 to 400.

13. The coated substrate of claim 12 , wherein each R 2 is selected from the group consisting of 4-bromophenyl and 4-hydroxyphenyl.

14. The coated substrate of claim 1 , wherein n is zero and the polytriazole polymer has a structure according to formula (III):

where:
R 1 is as defined in formula (I); and
the polytriazole polymer has a degree of polymerization from 100 to 200.

15. The coated substrate of claim 14 , wherein each R 1 is selected from the group consisting of
4-hydroxyphenyl,
4-fluorophenyl,
4-bromo-2,5-difluorophenyl,
3-(trifluoromethyl)phenyl,
2,5-difluorophenyl, and
2,3,4,5,6-pentafluorophenyl.

16. The coated substrate of claim 14 , wherein the polytriazole polymer has structure according to formula (IV):

where:
each R 1a and R 1b is a group R 1 as defined in formula (III);
R 1a is different from R 1b ; and
x+y=m.

17. The coated substrate of claim 16 , wherein R 1a and R 1b are independently selected from the group consisting of
4-bromophenyl,
4-hydroxyphenyl,
4-fluorophenyl,
2,4-difluorophenyl,
2,5-difluorophenyl,
4-bromo-2,5-difluorophenyl,
4-bromo-2,6-difluorophenyl,
2-bromo-4-fluorophenyl,
2,6-dibromo-4-fluorophenyl,
3-chloro-5-fluorophenyl,
3-chloro-4-fluorophenyl,
4-fluoro-3-(trifluoromethyl)phenyl,
3-(trifluoromethyl)phenyl,
3,5-dibromo-4-methylphenyl,
3-bromo-4-methylphenyl,
2,4,6-trimethylphenyl,
4-tert-butylphenyl,
4-(dimethylamino)phenyl,
2,3,4,5,6-pentafluorophenyl,
2,4,6-trifluorobenzyl,
3,4,5-trifluorobenzyl,
4-(trifluoromethyl)benzyl,
2,3,4-trifluorobenzyl,
4-fluorobenzyl,
3,5-(di-trifluoromethyl)benzyl,
2,4,6-trimethylbenzyl,
4-methylbenzyl,
4-carboxylbenzyl,
4-(triphenylmethyl)phenyl,
4-[tris(4-fluorophenyl)methyl]phenyl,
4-[tris(4-methylphenyl)methyl]phenyl,
4-[(4-hydroxyphenyl)diphenylmethyl]phenyl,
4-(triphenylmethyl)benzyl,
4-[tris(4-flu

Assignees

• Saudi Arabian Oil Co

Inventors

• Maab Husnul
• Alanazi Nayef M
• Al-Khaldi Turki A

Classifications

• C09D179/06 Primary

  Polyhydrazides; Polytriazoles; Polyamino-triazoles; Polyoxadiazoles · CPC title

• C08G73/0605 Primary

  Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms · CPC title

• C09D179/04

  Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors · CPC title