Thermally insulating composition for organic monolithic gel, use thereof and process for preparing same

Patent metadata

Field	Value
Publication number	US-10508436-B2
Application number	US-201314435617-A
Country	US
Kind code	B2
Filing date	Oct 8, 2013
Priority date	Oct 17, 2012
Publication date	Dec 17, 2019
Grant date	Dec 17, 2019

Abstract

Provided is a gelled carbon-based composition forming an organic polymeric monolithic gel capable of forming a porous carbon monolith by pyrolysis, a use thereof and a process for preparing this composition. A composition according to the invention is based on a resin derived at least partly from polyhydroxybenzene(s) R and formaldehyde(s) F, has a thermal conductivity of less than or equal to 40 mW·m −1 ·K −1 , and includes at least one water-soluble cationic polyelectrolyte P. A process for preparing this composition comprises: a) polymerization, in an aqueous solvent, of the polyhydroxybenzene(s) and formaldehyde(s), in the presence of at least one cationic polyelectrolyte dissolved in this solvent and of a catalyst, in order to obtain a solution based on the resin, b) gelling of the solution in order to obtain a gel, and c) drying in order to obtain the organic polymeric monolithic gel.

First claim

The invention claimed is:

1. A gelled carbon-based composition for forming an organic polymeric monolithic aerogel capable of forming a porous carbon monolith by pyrolysis, the composition being based on a resin derived from polyhydroxybenzene(s) R and formaldehyde(s) F,
wherein said gelled composition comprises at least one water-soluble cationic polyelectrolyte P, said gelled composition comprising the product of a polymerization reaction, in an aqueous solvent W, only of said polyhydroxybenzene(s) R and said formaldehyde(s) F, in the presence of said at least one cationic polyelectrolyte P dissolved in said solvent and of a catalyst,

wherein said gelled composition has:
a pore volume of between 0.1 cm 3 /g and 3 cm 3 /g,
a density of between 0.04 and 0.06,
a thermal conductivity from 10 to 35 mW·m −1 ·K −1 , measured at 22° C. with a Neotim conductivity meter according to the hot wire technique, and
at least one of a compression modulus of 800 MPa and a breaking strength of 25 MPa, measured in three-point compression and in tension with a MTS tensile/compression testing machine according to standard ASTM C165-07,
and
wherein the product of the polymerization reaction comprises said at least one cationic polyelectrolyte P in a mass fraction of between 0.2% and 2%.

2. The gelled carbon-based composition as claimed in claim 1 , wherein said product of the polymerization reaction comprises said at least one cationic polyelectrolyte P in a mass fraction of between 0.3% and 1%.

3. The gelled carbon-based composition as claimed in claim 1 , wherein said product of the polymerization reaction comprises said at least one cationic polyelectrolyte P in a P/(R+F+W) mass ratio with respect to said polyhydroxybenzene(s) R, formaldehyde(s) F and aqueous solvent W, which is between 0.3% and 2%.

4. The gelled carbon-based composition as claimed in claim 1 , wherein said at least one water-soluble cationic polyelectrolyte P is an organic polymer chosen from the group consisting of quaternary ammonium salts, poly(vinylpyridinium chloride), poly(ethyleneimine), poly(vinylpyridine), poly(allylamine hydrochloride), poly(trimethylammonium ethylmethacrylate chloride), poly(acrylamide-co-dimethylammonium chloride) and mixtures thereof.

5. The gelled carbon-based composition as claimed in claim 4 , wherein said at least one water-soluble cationic polyelectrolyte is a salt comprising units derived from a quaternary ammonium chosen from poly(diallyldimethylammonium halide).

6. The gelled carbon-based composition as claimed in claim 5 , wherein said at least one water-soluble cationic polyelectrolyte is a poly(diallyldimethylammonium chloride) or poly(diallyldimethylammonium bromide).

7. The gelled carbon-based composition as claimed in claim 1 , wherein said composition has:
a specific surface area of between 400 m 2 /g and 1200 m 2 /g, and/or
an average pore diameter of between 3 nm and 30 nm.

8. A process for preparing an organic polymeric monolithic aerogel, wherein said process comprises:
preparing the gelled carbon-based composition as claimed in claim 1 , wherein preparing the gelled carbon-based composition comprises:
a) polymerization, in an aqueous solvent W, of said polyhydroxybenzene(s) R and said formaldehyde(s) F, in the presence of said at least one cationic polyelectrolyte P dissolved in said solvent and of said catalyst, in order to obtain a solution based on said resin, and
b) gelling of the solution obtained in a) in order to obtain a gel of said resin, and

drying of the gel obtained in b) in order to obtain said organic polymeric monolithic aerogel.

9. The preparation process as claimed in claim 8 , wherein the step a) is carried out by using said at least one cationic polyelectrolyte P:
in a mass fraction in the composition of between 0.2% and 2%, and/or
in a P/(R+F) mass ratio with respect to said polyhydroxybenzene(s) R and said formaldehyde(s) F, of between 2% and 10%, and/or
in a P/(R+F+W) mass ratio with respect to said polyhydroxybenzene(s) R, said formaldehyde(s) F and said aqueous solvent W, of between 0.3% and 2%.

10. The preparation process as claimed in claim 8 , wherein:
the step a) is carried out at ambient temperature, by dissolving said polyhydroxybenzene(s) R and said at least one cationic polyelectrolyte P in said aqueous solvent, and then by adding, to the solution obtained, said formaldehyde(s) F and said acidic or basic catalyst, then
the step b) is carried out by curing said solution in an oven.

11. The preparation process as claimed in claim 8 , wherein the step of drying the gel is carried out by drying with humid air, without solvent exchange or drying with supercritical fluid, in order to obtain said organic polymeric monolithic gel which has:
a specific surface area of between 400 m 2 /g and 1200 m 2 /g, and/or
an average pore diameter of between 3 nm and 30 nm.

12. The preparation process as claimed in claim 8 , wherein the pH of the solution obtained in the step a) is adjusted to 1 with the catalyst which is acidic, so that the density of the organic polymeric monolithic aerogel is of between 0.04 and 0.06.

13. A method of insulating a building comprising a step of installing the composition as claimed in claim 1 in a building as a thermal insulation.

Assignees

• Hutchinson

Inventors

• Swoboda Benjamin
• Dufour Bruno
• Sonntag Philippe
• Dominiak Christophe

Classifications

• C08J2361/12

  with polyhydric phenols · CPC title

• C08J2205/042

  Nanopores, i.e. the average diameter being smaller than 0,1 micrometer · CPC title

• C08J2205/028

  Xerogel, i.e. an air dried gel · CPC title

• C08J2201/0504

  the liquid phase being aqueous · CPC title

• C08J2201/0484

  the liquid phase being aqueous · CPC title