Photomechanically active copolyimides derived from an azobenzenediamine, a rigid dianhydride, and a flexible dianhydride

Patent metadata

Field	Value
Publication number	US-9834644-B1
Application number	US-201514723807-A
Country	US
Kind code	B1
Filing date	May 28, 2015
Priority date	Oct 26, 2012
Publication date	Dec 5, 2017
Grant date	Dec 5, 2017

Abstract

Compositions of azobenzene-containing, photomechanically active, copoly(amic acids) and linear copolyimides including an azobenzenediamine, a rigid dianhydride, and a flexible dianhydride are provided; and methods of making the same.

First claim

What is claimed is:

1. The photomechanical polymer, wherein the photomechanical polymer is the copoly(amic acid) having photomechanical properties and comprising the azobenzenediamine, the rigid dianhydride, and the flexible dianhydride, the copoly(amic acid) having a general formula:

wherein Ar is at least one of 1,2,4,5-benzene (pyromellitic), 1,4,5,8-naphthalene, and 3,3′,4,4′-biphenyl;
wherein R is at least one of —C(CF 3 ) 2 —, —O—, >C═O, >SO 2 , —OPh-C(CF 3 ) 2 -PhO—, —OPh-C(CH 3 ) 2 -PhO—, >C(CF 3 )Ph, —O(1,3-Ph)O—, and —O(1,4-Ph)O—;
wherein R′ and R″ are —H, —F, —Cl, or —CH 3 when R′ and R″ are identical, or wherein R′ is —H and R″ is at least one of —F, —Cl, —CH 3 , —CF 3 , and —OCH 3 when R′ and R″ are different; and
wherein 0.05≦x≦0.75.

2. The photomechanical polymer of claim 1 , wherein 0.05≦x≦0.50.

3. The photomechanical polymer of claim 1 , wherein 0.25≦x≦0.75.

4. The photomechanical polymer of claim 1 , wherein 0.50≦x≦0.75.

5. The photomechanical polymer of claim 1 , wherein n is between 100 and 500.

6. The photomechanical polymer of claim 1 , wherein the azobenzenediamine comprises at least one of 4,4′-diaminoazobenzene; 3-fluoro-4,4′-diaminoazobenzene; 3-chloro-4,4′-diaminoazobenzene; 3-methyl-4,4′-diaminoazobenzene; 3-trifluormethyl-4,4′-diaminoazobenzene; 3-methoxy-4,4′-diaminoazobenzene; 3,3′-fluoro-4,4′-diaminoazobenzene; 3,3′-chloro-4,4′-diaminoazobenzene; or 3,3′-methyl-4,4′-diaminoazobenzene.

7. The photomechanical polymer of claim 1 , wherein the flexible dianhydride comprises at least one of 2,2-bis(phthalic anhydride)-1,1,1,3,3,3-hexafluoroisopropane; 4,4′-oxydi(phthalic anhydride); 3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride; 3,3′,4,4′-benzophenone tetracarboxylic dianhydride; 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride; 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride; 4,4′-(2,2,2-trifluoro-1-phenylethylidene)diphthalic anhydride; 2,2′4,4′-(p-phenylenedioxy)diphthalic anhydride; or 4,4′-(m-phenylenedioxy)diphthalic anhydride.

8. The photomechanical polymer of claim 1 , wherein the rigid dianhydride comprises at least one of pyromellitic dianhydride; 1,4,5,8-naphthalenetetracarboxylic acid dianhydride; or 1,1′-biphenyl-3,3′,4,4′-tetracarboxylic acid dianhydride.

9. The photomechanical polymer of claim 1 , wherein the azobenzenediamine is 4,4′-diaminoazobenzene; the flexible dianhydride is 2,2-bis(phthalic anhydride)-1,1,1,3,3,3-hexafluoroisopropane; and the rigid dianhydride is pyromellitic dianhydride.

10. The photomechanical polymer, wherein the photomechanical polymer is the copolyimide having photomechanical properties and comprising the azobenzenediamine, the rigid dianhydride, and the flexible dianhydride, the copolyimide having the general formula:

wherein Ar is at least one of 1,2,4,5-benzene (pyromellitic), 1,4,5,8-naphthalene, or 3,3′,4,4′-biphenyl;
wherein R is at least one of —C(CF 3 ) 2 —, —O—, >C═O, >SO 2 , —OPh-C(CF 3 ) 2 -PhO—, —OPh-C(CH 3 ) 2 -PhO—, >C(CF 3 )Ph, —O(1,3-Ph)O—, or —O(1,4-Ph)O—;
wherein R′ and R″ are —H, —F, —Cl, or —CH 3 when R′ and R″ are identical, or wherein R′ is —H and R″ is at least one of —F, —Cl, —CH 3 , —CF 3 , or —OCH 3 when R′ and R″ are different; and
wherein 0.25≦x≦0.75.

11. The photomechanical polymer of claim 10 , wherein 0.50≦x≦0.75.

12. The photomechanical polymer of claim 10 , wherein n is between 100 and 500.

13. The photomechanical polymer of claim 10 , wherein the azobenzenediamine comprises at least one of 4,4′-diaminoazobenzene; 3-fluoro-4,4′-diaminoazobenzene; 3-chloro-4,4′-diaminoazobenzene; 3-methyl-4,4′-diaminoazobenzene; 3-trifluormethyl-4,4′-diaminoazobenzene; 3-methoxy-4,4′-diaminoazobenzene; 3,3′-fluoro-4,4′-diaminoazobenzene; 3,3′-chloro-4,4′-diaminoazobenzene; or 3,3′-methyl-4,4′-diaminoazobenzene.

14. The photomechanical polymer of claim 13 , wherein the flexible dianhydride comprises at least one of 2,2-bis(phthalic anhydride)-1,1,1,3,3,3-hexafluoroisopropane; 4,4′-oxydi(phthalic anhydride); 3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride; 3,3′,4,4′-benzophenone tetracarboxylic dianhydride; 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride; 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride; 4,4′-(2,2,2-trifluoro-1-phenylethylidene)diphthalic anhydride; 2,2′4,4′-(p-phenylenedioxy)diphthalic anhydride; or 4,4′-(m-phenylenedioxy)diphthalic anhydride.

15. The photomechanical polymer of claim 10 , wherein the rigid dianhydride comprises at least one of pyromellitic dianhydride; 1,4,5,8-naphthalenetetracarboxylic acid dianhydride; or 1,1′-biphenyl-3,3′,4,4′-tetracarboxylic acid dianhydride.

16. The photomechanical polymer of claim 10 , wherein the azobenzenediamine is 4,4′-diaminoazobenzene; the flexible dianhydride is 2,2-bis(phthalic anhydride)-1,1,1,3,3,3-hexafluoroisopropane; and the rigid dianhydride is pyromellitic dianhydride.

Assignees

• Us Air Force
• Us Air Force

Inventors

• Tan Loon-Seng
• Wang David Huabin
• Lee Kyung Min
• White Timothy J

Classifications

• C08G73/1067 Primary

  Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound · CPC title

• C08G69/42

  Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen (C08G69/12, C08G69/32 take precedence) · CPC title

• C08G73/1039

  comprising halogen-containing substituents · CPC title

• C08G73/1007

  from tetracarboxylic acids or derivatives and diamines · CPC title

• C08G73/1096

  containing azo linkage in the main chain · CPC title