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

• US 9,822,088 B2
• Filed: 11/01/2011
• Issued: 11/21/2017
• Est. Priority Date: 03/30/2011
• Status: Active Grant

• Current Assignee: United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration
• Original Assignee: United States of America as represented by the Administrator of NASA
• Inventors: Wohl, Christopher J., Connell, John W., Siochi, Emilie J., Smith, Joseph G.
• Primary Examiner(s): Stanley, Jane L
• Application Number:
  US13/286,715
• Publication Number:
  US 20120252968A1
• Time in Patent Office: 2,212 Days
• Field of Search: 524600
• CPC Class Codes: C07D 305/08 with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring atoms
• CPC Class Codes: C08G 63/68 Polyesters containing atoms other than carbon, hydrogen and oxygen C08G63/64 takes precedence
• CPC Class Codes: C08G 65/16 Cyclic ethers having four or more ring atoms
• CPC Class Codes: C08G 65/18 Oxetanes
• CPC Class Codes: C08G 65/322 containing hydrogen
• CPC Class Codes: C08G 65/33389 aromatic
• CPC Class Codes: C08G 73/02 Polyamines
• CPC Class Codes: C08G 73/1042 Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
• CPC Class Codes: C08G 73/105 with oxygen only in the diamino moiety
• CPC Class Codes: C08L 67/00 Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain of polyester-amides C08L77/12; of polyester-imides C08L79/08; Compositions of derivatives of such polymers
• CPC Class Codes: C09D 179/08 Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

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.

Claims

1. An oligomer represented by the formula:

(E)_yR¹—

C(O)—

O-J-C(O)—

R¹(E)_y

wherein;

J is [CH₂—

CR²R³—

CH₂—

O]_m or

[(CH₂—

CR²R³—

CH₂—

O)_p—

(R⁶—

O)_q—

(CH₂—

CR²R³—

CH₂—

O)_r] wherein R⁶ is substituted or unsubstituted aliphatic or aromatic moiety of 2 to 16 carbons;

E, which is the same or different, is —

NO₂ or —

NH₂;

y is 1 or 2;

R¹, 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 R² is —

F; and

R³, which is the same or different, is chosen from —

F, —

R⁴H_(n-a)F_a, —

R⁵—

O—

R⁴H_(n-a)F_a, and —

O—

R⁴H_(n-a)F_a, wherein R⁴ is an alkyl or ether moiety of 1 to 30 carbons, R⁵ 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

R², which is the same or different, is —

H, —

F, or alkyl of 1 to 6 carbon atoms; and

R³, which is the same or different, is chosen from —

F and —

O—

R⁴H_(n-a)F_a, wherein R⁴ 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 R⁴ 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 R² is methyl.

5. The oligomer of claim 3 wherein R¹ is phenyl.

6. The oligomer of claim 3 wherein R⁵ is —

CH₂—

O—

C(X)₂—

CF₃, wherein X is —

H or —

F.

7. The oligomer of claim 3 wherein E is —

NO₂.

8. The oligomer of claim 3 wherein E is —

NH₂.

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 —

NH₂.

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 —

NH₂.

11. The oligomer of claim 1, wherein R² is —

F.