Low density, resorcinol-formaldehyde aerogels

• US 4,873,218 A
• Filed: 05/26/1988
• Issued: 10/10/1989
• Est. Priority Date: 05/26/1988
• Status: Expired due to Term

• Current Assignee: Lawrence Livermore National Security LLC (Government of the United States of America)
• Original Assignee: United States Department of Energy
• Inventors: Pekala, Richard W.
• Primary Examiner(s): Foelak, Morton
• Application Number:
  US07/199,404
• Time in Patent Office: 502 Days
• Field of Search: 502/418, 502/437, 521/64, 521/181
• US Class Current: 502/418
• CPC Class Codes: B01J 20/20 comprising free carbon; comprising carbon obtained by carbonising processes
• CPC Class Codes: C08G 8/20 with polyhydric phenols

Abstract

The polycondensation of resorcinol with formaldehyde under alkaline conditions results in the formation of surface functionalized polymer "clusters". The covalent crosslinking of these "clusters" produces gels which when processed under supercritical conditions, produce low density, organic aerogels (density ≦100 mg/cc; cell size ≦0.1 microns). The aerogels are transparent, dark red in color and consist of interconnected colloidal-like particles with diameters of about 100 Å. These aerogels may be further carbonized to form low density carbon foams with cell size of about 0.1 micron.

Claims

1. A process for the synthesis of a low density, organic aerogel of ultra-fine pore size, said process comprising the steps of:

mixing in a predetermined ratio a polyhydroxy benzene and formaldehyde in the presence of a base catalyst;

heating the mixture to a predetermined temperature for a sufficiently long period of time to form a stable gel;

washing the gel in a suitable organic solvent to exchange the aqueous solvent for the organic solvent;

critical point drying the gel; and

characterizing the gel.

2. The process of claim 1, wherein the pH of said mixture is in the range of about 6.5 to about 7.4.

3. The process of claim 2, wherein the polyhydroxy benzene is a dihydroxy benzene.

4. The process of claim 3, wherein said dihydroxy benzene is selected from the group consisting of resorcinol, catechol, substituted resorcinol, substituted catechol and mixtures thereof.

5. The process of claim 4, wherein said dihydroxy benzene is resorcinol.

6. The process of claim 5, wherein said solvent is selected from the group consisting of methanol, acetone, isopropanol and amyl acetate.

7. The process of claim 6, wherein said solvent is acetone.

8. The process of claim 7, wherein the ratio of said resorcinol to said formaldehyde is about 1:

2.

9. The process of claim 8, wherein said base catalyst is sodium carbonate.

10. The process of claim 9, further comprising the step of heating said aerogel in a nitrogen atmosphere, to a temperature in the range of about 600°

to about 1200°

C. to carbonize said aerogel and form a low density, carbon foam.

11. The process of claim 4, wherein said dihydroxy benzene is a mixture of resorcinol and catechol.

12. The process of claim 4, wherein said dihydroxy benzene is a mixture of resorcinol and hydroquinone.

13. The process of claim 4, wherein said dihydroxy benzene is a mixture of resorcinol and phloroglucinol.

14. A process for the synthesis of a low density, microcellular resorcinol-formaldehyde aerogel, said process comprising the steps of:

(a) mixing resorcinol and formaldehyde in a molar ratio of about 1;

2, in the presence of catalytic amounts of sodium carbonate;

(b) adjusting the pH of the mixture to a value in the range of about 6.5 to about 7.4;

(c) decanting the mixture into a glass ampoule;

(d) sealing the glass ampoule;

(e) heating the mixture to about 85°

C. in an oven for about seven days to facilitate formation of a gel;

(f) removing the ampoule from the oven and cooling it to room temperature;

(g) breaking the ampoule and removing the gel from the ampoule;

(h) washing the gel in an agitated bath of trifluoracetic acid at 45°

C. for three days;

(i) transferring the gel from the acid bath to an agitated acetone bath maintained at about 45°

C., to remove water;

(j) removing the gel from the acetone bath and critical point drying the gel; and

(k) characterizing the gel.

15. The process of claim 14, further comprising the step of heating said aerogel in a nitrogen atmosphere to a temperature in the range of about 600°

to about 1200°

C. to carbonize said aerogel and form a low density, carbon foam.