Flexible composite aerogel and process for producing same
The present invention relates to a flexible composite organic aerogel ( 1 ) comprising: a textile reinforcement ( 5 ), an organic aerogel ( 3 ) placed within said textile reinforcement ( 3 ), said organic aerogel ( 3 ) being based on a resin resulting at least in part from polyhydroxybenzene(s) R and formaldehyde(s) F, said organic aerogel ( 3 ) being a polymeric organic gel comprising at least one water-soluble cationic polyelectrolyte, or said organic aerogel ( 3 ) being a pyrolysate of said gel in the form of a porous carbon monolith comprising the product of the pyrolysis of said at least one water-soluble cationic polyelectrolyte P, said organic aerogel ( 3 ) exhibiting a specific thermal conductivity of between 10 and 40 mW·m −1 ·K −1 at atmospheric pressure.
1. A flexible composite organic aerogel, comprising:
a textile reinforcement; and
an organic aerogel placed within the textile reinforcement,
wherein:
the organic aerogel is based on a resin resulting at least in part from at least one polyhydroxybenzene R and at least one formaldehyde F; and
the organic aerogel is:
(i) a polymeric organic gel comprising at least one water-soluble cationic polyelectrolyte P, or
(ii) the organic aerogel is a pyrolysate of the polymeric organic gel in the form of a porous carbon monolith comprising a product of pyrolysis of the at least one water-soluble cationic polyelectrolyte P,
wherein the at least one water-soluble cationic polyelectrolyte P is an organic polymer selected from the group consisting of a quaternary ammonium salt, a poly(vinylpyridinium chloride), a polyethyleneimine, a polyvinylpyridine, a poly(allylamine hydrochloride), a poly(trimethylammonioethyl methacrylate chloride), a poly(acrylamide-co-dimethylammonium chloride) and mixtures thereof; and
the organic aerogel exhibits a specific thermal conductivity of between 10 and 40 mW·m −1 ·K −1 at atmospheric pressure,
wherein the flexible composite organic aerogel comprises a product of a polymerization reaction in an aqueous solvent W of the at least one polyhydroxybenzene R and the at least one formaldehyde F, in the presence of the at least one water-soluble cationic polyelectrolyte P dissolved in the aqueous solvent W and in the presence of a catalyst,
wherein the product of the polymerization reaction comprises the at least one water-soluble cationic polyelectrolyte P in a ratio by weight according to P/(R+F) of 2% to 10%, with respect to the at least one polyhydroxybenzene R and the at least one formaldehyde F, and
wherein the organic aerogel has a density of between 0.01 and 0.4 g/cm 3 .
2. The flexible composite organic aerogel of claim 1 , wherein the at least one water-soluble cationic polyelectrolyte P is a salt comprising units resulting from a quaternary ammonium of a poly(diallyldimethylammonium halide).
3. The flexible composite organic aerogel of claim 1 , wherein the product of the polymerization reaction comprises 0.2% to 2% mass fraction of the at least one water-soluble cationic polyelectrolyte P.
4. The flexible composite organic aerogel of claim 1 , wherein the product of the polymerization reaction comprises the at least one water-soluble cationic polyelectrolyte P in a ratio by weight according to P/(R+F+W) ratio by weight of 0.3% to 2%, with respect to the polyhydroxybenzene R, the at least one formaldehyde R and the aqueous solvent W %.
5. The flexible composite organic aerogel of claim 1 , wherein the organic aerogel further exhibits at least one of the following properties:
a specific surface of between 400 m 2 /g and 1200 m 2 /g;
a pore volume of between 0.1 cm 3 /g and 3 cm 3 /g;
a mean pore diameter of between 3 nm and 30 nm.
6. The flexible composite organic aerogel of claim 1 , wherein, when the organic aerogel is the polymeric organic gel comprising the at least one water-soluble cationic polyelectrolyte P, the textile reinforcement is produced with organic fibers having a moisture uptake content of greater than or equal to 5% and having a chemical affinity for the said organic aerogel.
7. The flexible composite organic aerogel of claim 6 , wherein the organic fibers or filaments of the textile reinforcement are selected from the group consisting of
a meta-aramid fiber,
an oxidized polyacrylonitrile fiber,
a polyamide-imide fiber,
a phenolic fiber,
a polybenzimidazole fiber, and
a polysulfonamide fiber.
8. The flexible composite organic aerogel of claim 6 , wherein the textile reinforcement is a nonwoven textile.
9. The flexible composite organic aerogel of claim 6 , wherein the textile reinforcement is a woven textile.
10. The flexible composite organic aerogel of claim 6 , wherein the textile reinforcement is a textile in three dimensions.
11. The flexible composite organic aerogel of claim 1 , wherein, when the organic aerogel is a pyrolysate in the form of a porous carbon monolith comprising the product of the pyrolysis of the at least one water-soluble cationic polyelectrolyte P, the textile reinforcement is produced with inorganic fibers which are resistant to the pyrolysis temperature.
12. The flexible composite organic aerogel of claim 11 , wherein the inorganic fibers or filaments of the textile reinforcement are selected from the group consisting of
a glass fiber,
a basalt fiber,
a ceramic fiber,
a silica fiber, and
a silicon carbide fiber.
13. A process for manufacturing the flexible composite organic aerogel of claim 1 , the process comprising:
a) polymerizing at least one polyhydroxybenzene R and at least one formaldehyde F in an aqueous solvent W, in the presence of at least one cationic polyelectrolyte P dissolved in the aqueous solvent W and in the presence of a catalyst, said polymerizing occurring within the textile reinforcement, to obtain a solution;
b) gelling the solution within the textile reinforcement in order to obtain a gel; and
c) drying of the textile reinforcement impregnated with the gel obtained in b) to obtain a dried gel,
wherein the at least one water-soluble cationic polyelectrolyte P is an organic polymer selected from the group consisting of a quaternary ammonium salt, a poly(vinylpyridinium chloride), a polyethyleneimine, a polyvinylpyridine, a poly(allylamine hydrochloride), a poly(trimethylammonioethyl methacrylate chloride), a poly(acrylamide-co-dimethylammonium chloride) and mixtures thereof,
wherein the at least one water-soluble cationic polyelectrolyte P is used
according to a P/(R+F) ratio by weight, with respect to the polyhydroxybenzene R and formaldehyde F, of between 2% and 10%.
14. The manufacturing process of claim 13 , further comprising pyrolyzing the dried gel, in order to obtain a porous carbon.
15. The manufacturing process of claim 13 , wherein:
the polymerizing a) occurs at ambient temperature, by
dissolving the at least one polyhydroxylbenzene R and the at least one water-soluble cationic polyelectrolyte P in the aqueous solvent W, and then adding, to the solution, the at least one formaldehyde F and an acidic or basic catalyst, before pouring the solution over the textile reinforcement; and
the gelling b) occurs by curing impregnated textile reinforcement in an oven.
16. The manufacturing process of claim 13 , wherein the drying c) occurs by drying with air in order to obtain a polymeric organic gel further exhibiting at least one of the following conditions:
a specific surface of between 400 m 2 /g and 1200 m 2 /g;
a pore volume of between 0.1 cm 3 /g and 3 cm 3 /g;
a mean pore diameter of between 3 nm and 30 nm.