Anisotropic copoly(imide oxetane) coatings and articles of manufacture, copoly(imide oxetane)s containing pendant fluorocarbon moieties, oligomers and processes therefor

Patent metadata

Field	Value
Publication number	US-9822088-B2
Application number	US-201113286715-A
Country	US
Kind code	B2
Filing date	Nov 1, 2011
Priority date	Mar 30, 2011
Publication date	Nov 21, 2017
Grant date	Nov 21, 2017

Abstract

Copoly(imide oxetane) materials are disclosed that can exhibit a low surface energy while possessing the mechanical, thermal, chemical and optical properties associated with polyimides. The copoly(imide oxetane)s are prepared using a minor amount of fluorinated oxetane-derived oligomer with sufficient fluorine-containing segments of the copoly(imide oxetane)s that migrate to the exterior surface of the polymeric material to yield low surface energies. Thus the coatings and articles of manufacture made with the copoly(imide oxetane)s of this invention are characterized as having an anisotropic fluorine composition. The low surface energies can be achieved with very low content of fluorinated oxetane-derived oligomer. The copolymers of this invention can enhance the viability of polyimides for many applications and may be acceptable where homopolyimide materials have been unacceptable.

First claim

It is claimed:

1. An oligomer represented by the formula:
(E) y R 1 —C(O)—O-J-C(O)—R 1 (E) y

wherein:
J is [CH 2 —CR 2 R 3 —CH 2 —O] m or
[(CH 2 —CR 2 R 3 —CH 2 —O) p —(R 6 —O) q —(CH 2 —CR 2 R 3 —CH 2 —O) r ] wherein R 6 is substituted or unsubstituted aliphatic or aromatic moiety of 2 to 16 carbons;
E, which is the same or different, is —NO 2 or —NH 2 ;
y is 1 or 2;
R 1 , which is the same, is aromatic hydrocarbon moiety of 1 to 10 carbon atoms;
m is between about 4 and 500, p is between about 4 and 150, q is between about 1 and 150, and r is an integer; and
either R 2 is —F; and
R 3 , which is the same or different, is chosen from —F, —R 4 H (n-a) F a , —R 5 —O—R 4 H (n-a) F a , and —O—R 4 H (n-a) F a , wherein R 4 is an alkyl or ether moiety of 1 to 30 carbons, R 5 is an alkyl moiety of 1 to 30 carbons, a is an integer of 3 to n, and n is twice the number of carbon atoms in the alkyl moiety plus 1; or
R 2 , which is the same or different, is —H, —F, or alkyl of 1 to 6 carbon atoms; and
R 3 , which is the same or different, is chosen from —F and —O—R 4 H (n-a) F a , wherein R 4 is an alkyl or ether moiety of 1 to 30 carbons, a is an integer of 3 to n, and n is twice the number of carbon atoms in the alkyl moiety plus 1.

2. The oligomer of claim 1 wherein the omega carbon of R 4 has three fluoride substituents.

3. The oligomer of claim 2 wherein m is between 6 and 100.

4. The oligomer of claim 3 wherein y is 1 and R 2 is methyl.

5. The oligomer of claim 3 wherein R 1 is phenyl.

6. The oligomer of claim 3 wherein R 5 is —CH 2 —O—C(X) 2 —CF 3 , wherein X is —H or —F.

7. The oligomer of claim 3 wherein E is —NO 2 .

8. The oligomer of claim 3 wherein E is —NH 2 .

9. A copoly(imide oxetane) containing 0.001 to 15 mass percent of the oligomer of claim 1 as a reactant product wherein E is —NH 2 .

10. The copoly(imide oxetane) of claim 9 containing 0.001 to 0.1 mass percent of the oligomer of claim 1 wherein E is —NH 2 .

11. The oligomer of claim 1 , wherein R 2 is —F.

Assignees

• Wohl Christopher J
• Connell John W
• Siochi Emilie J
• Smith Joseph G
• Nasa

Inventors

• Wohl Christopher J
• Connell John W
• Siochi Emilie J
• Smith Joseph G

Classifications

• C09D179/08

  Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors · CPC title

• C08G73/1042

  Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds · CPC title

• C08G65/33389

  aromatic · CPC title

• C08G65/322

  containing hydrogen · CPC title

• C08G65/18

  Oxetanes · CPC title