Multi(azobenzene-amine) photoactive crosslinkers and methods of making the same

Patent metadata

Field	Value
Publication number	US-9255065-B1
Application number	US-201313866524-A
Country	US
Kind code	B1
Filing date	Apr 19, 2013
Priority date	Apr 20, 2012
Publication date	Feb 9, 2016
Grant date	Feb 9, 2016

Abstract

Photo-active cross-linkers derived from a tris(azobenzene)-containing compound with the following generic structure:

wherein for meta-azo substitution, R is equal to H, and for para-azo substitution, R is selected from the group consisting of H, F, Cl, CF 3 , and CH 3 .

First claim

What is claimed is:

1. A tris(azobenzene-amine) cross-linker with the following structure:

wherein for meta-azo substitution, R is equal to H, and for para-azo substitution, R is selected from the group consisting of H, F, Cl, CF 3 , and CH 3 .

2. A method for making the tris(azobenzene-amine) cross-linker of claim 1 comprising the steps:
providing 1,1,1,-tris(4-hydroxyphenyl)ethane;
treating the 1,1,1,-tris(4-hydroxyphenyl)ethane with a nitro-activated aryl halide in presence of potassium carbonate to produce a tris[(nitrophenoxy)phenyl]ethane compound;
reducing the tris[(nitrophenoxy)phenyl]ethane compound to a tris[(acetamidophenoxy)phenyl]ethane compound by catalytic hydrogenation;
treating the tris[(acetamidophenoxy)phenyl]ethane compound with 4-nitrosoacetanilide in acetic acid to yield a tris(azobenzene-amide) compound; and
converting amides in the tris(azobenzene-amide) compound to amines via an alkaline deacetylation reaction to form the tris(azobenzene-amine) cross-linker.

3. The method for making the tris(azobenzene-amine) cross-linker of claim 2 wherein the nitro-activated aryl halide is 1-fluoro-4-nitrobenzene and the tris[(nitrophenoxy)phenyl]ethane compound is 1,1,1-tris[4-(4-nitrophenoxy)phenyl]ethane.

4. The method for making the tris(azobenzene-amine) cross-linker of claim 2 wherein the nitro-activated aryl halide is 1,2-difluoro-4-nitrobenzene and the tris[(nitrophenoxy)phenyl]ethane compound is 1,1,1-tris[4-(4-nitrophenoxy)phenyl]ethane.

5. The method for making the tris(azobenzene-amine) cross-linker of claim 2 wherein the nitro-activated aryl halide is 2-chloro-1-fluoro-4-nitrobenzene, and the tris[(nitrophenoxy)phenyl]ethane compound is 1,1,1-tris[4-(4-nitrophenoxy)phenyl]ethane.

6. The method for making the tris(azobenzene-amine) cross-linker of claim 2 wherein the nitro-activated aryl halide is 1-fluoro-4-nitro-2-(trifluoromethyl)benzene, and the tris[(nitrophenoxy)phenyl]ethane compound is 1,1,1-tris[4-(4-nitrophenoxy)phenyl]ethane.

7. The method for making the tris(azobenzene-amine) cross-linker of claim 2 wherein the nitro-activated aryl halide is 1-fluoro-2-methyl-4-nitrobenzene, and the tris[(nitrophenoxy)phenyl]ethane compound is 1,1,1-tris[4-(4-nitrophenoxy)phenyl]ethane.

Assignees

• Us Of America As Represented By The Secretary Of The Air Force
• Us Air Force

Inventors

• Tan Loon-Seng
• Wang David Huabin

Classifications

• C07C245/08 Primary

  with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene · CPC title

• C07F9/5325

  Aromatic phosphine oxides or thioxides (P-C aromatic linkage) · CPC title

• C07C217/90 Primary

  the oxygen atom of at least one of the etherified hydroxy groups being further bound to a carbon atom of a six-membered aromatic ring, e.g. amino-diphenylethers · CPC title

• C08G73/1085

  Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties · CPC title