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

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.Math.m.sup.1.Math.K.sup.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.

Claims

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.sup.3/g and 3 cm.sup.3/g, a density of between 0.04 and 0.06, a thermal conductivity from 10 to 35 mW.Math.m.sup.1.Math.K.sup.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.sup.2/g and 1200 m.sup.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.sup.2/g and 1200 m.sup.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.

Description

DETAILED DESCRIPTION

(1) The term gel is intended to mean, in a known manner, the mixture of a colloidal material and of a liquid, which forms spontaneously or under the action of a catalyst by flocculation and coagulation of a colloidal solution.

(2) The term water-soluble polymer is intended to mean a polymer which can be dissolved in water without the addition of additives (in particular surfactants), unlike a water-dispersible polymer which is capable of forming a dispersion when it is mixed with water.

(3) According to another characteristic of the invention, said carbon-based composition comprises the product of a reaction for polymerization, in an aqueous solvent W of said polyhydroxybenzene(s) R and formaldehyde(s) F, in the presence of said at least one cationic polyelectrolyte P dissolved in this solvent and of an acid or basic catalyst.

(4) Advantageously, said product of the polymerization reaction may comprise: said at least one cationic polyelectrolyte P in a very low mass fraction which is between 0.2% and 2% and preferably between 0.3% and 1%, and/or said at least one cationic polyelectrolyte P in a P/(R+F) mass ratio with respect to said polyhydroxy-benzene(s) R and formaldehyde(s) F, which is between 2% and 10% and preferably between 3% and 7%, and/or said at least one cationic polyelectrolyte P in a P/(R+F+W) mass ratio with respect to said polyhydroxy-benzene(s) R, formaldehyde(s) F and aqueous solvent W, which is between 0.3% and 2% and preferably between 0.4% and 1.5%.

(5) Said at least one polyelectrolyte may be any cationic polyelectrolyte which is totally soluble in water and has a low ionic strength.

(6) Preferably, it 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.

(7) Even more preferentially, said at least one water-soluble cationic polyelectrolyte P is a salt comprising units derived from a quaternary ammonium chosen from poly(diallyldimethylammonium halide) and is preferably poly(diallyldimethylammonium chloride) or poly(diallyldimethylammonium bromide).

(8) Among the precursor polymers of said resin which are usable in the present invention, mention may be made of polymers resulting from the polycondensation of at least one monomer of the polyhydroxybenzene type and of at least one formaldehyde monomer. This polymerization reaction may involve more than two distinct monomers, the additional monomers optionally being of the polyhydroxybenzene type. The polyhydroxybenzenes that are usable are preferentially di- or tri-hydroxybenzenes, and advantageously resorcinol (1,3-dihydroxybenzene) or a mixture of resorcinol with another compound chosen from catechol, hydroquinone and phloroglucinol.

(9) Use may, for example, be made of the polyhydroxy-benzene(s) R and formaldehyde(s) F according to an R/F molar ratio of between 0.3 and 0.7.

(10) According to another characteristic of the invention, said carbon-based composition may advantageously have a specific surface area of between 400 m.sup.2/g and 1200 m.sup.2/g, and/or a pore volume of between 0.1 cm.sup.3/g and 3 cm.sup.3/g, and/or an average pore diameter of between 3 nm and 30 nm, and/or a density of between 0.04 and 0.4.

(11) An organic polymeric monolithic gel according to the invention, such as an aerogel, consists of a carbon-based composition as defined above.

(12) Advantageously, this gel and the carbon monolith obtained via its pyrolysis may have a thermal conductivity of between 10 mW.Math.m.sup.1.Math.K.sup.1 and 40 mW.Math.m.sup.1.Math.K.sup.1 and for example of between 20 and 35 mW.Math.m.sup.1.Math.K.sup.1, this gel being usable for thermal insulation of a building.

(13) A process according to the invention for preparing a carbon-based composition as defined above comprises:

(14) a) polymerization, in an aqueous solvent W, of said polyhydroxybenzene(s) R and formaldehyde(s) F, in the presence of said at least one cationic polyelectrolyte P dissolved in this solvent and of a catalyst, in order to obtain a solution based on said resin,

(15) b) gelling of the solution obtained in a) in order to obtain a gel of said resin, and

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

(17) In order to obtain the porous carbon monolith, the dried gel obtained in c) is subjected to pyrolysis.

(18) Advantageously and as indicated above, step a) may be carried out using said at least one polyelectrolyte P in a mass fraction in the composition of between 0.2% and 2%, and/or in a P/(R+F) mass ratio of between 2% and 10%, and/or in a P/(R+F+W) mass ratio of between 0.3% and 2%.

(19) Likewise advantageously, it is possible to carry out: step a) at ambient temperature, by dissolving said polyhydroxybenzene(s) R and said at least one cationic polyelectrolyte P in said aqueous solvent, preferably consisting of water, and then by adding, to the solution obtained, said formaldehyde(s) F and said catalyst which may be acidic or basic, then step b) by curing said solution in an oven.

(20) By way of catalyst usable in step a), mention may, for example, be made of acidic catalysts, such as aqueous solutions of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, phosphoric acid, trifluoroacetic acid, trifluoromethanesulfonic acid, perchloric acid, oxalic acid, toluenesulfonic acid, dichloroacetic acid or formic acid, or else basic catalysts such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, ammonium carbonate, lithium carbonate, aqueous ammonia, potassium hydroxide and sodium hydroxide.

(21) Use may, for example, be made, in step a), of an R/W mass ratio between polyhydroxybenzene(s) and water of between 0.001 and 0.07.

(22) Preferably, step c) is carried out by drying in humid air, for example in an oven, without solvent exchange or drying with supercritical fluid, in order to obtain said organic polymeric monolithic gel which has (according to the synthesis conditions and in particular the pH) a specific surface area of between 400 m.sup.2/g and 1200 m.sup.2/g, and/or a pore volume of between 0.1 cm.sup.3/g and 3 cm.sup.3/g, and/or an average pore diameter of between 3 nm and 30 nm, and/or a density of between 0.04 and 0.4.

(23) It will be noted that this aqueous-phase preparation process according to the invention thus makes it possible to obtain controlled porous structures which vary according to the synthesis conditions. It is thus possible to obtain a structure of low density that is solely nanoporous (i.e. with a pore diameter of less than 50 nm), or alternatively with a coexistence between nanopores and macropores (i.e. with a pore diameter of greater than 50 nm).

(24) Other characteristics, advantages and details of the present invention will emerge on reading the following description of several implementation examples of the invention, given by way of nonlimiting illustration.

EXAMPLES OF PREPARATION ACCORDING TO THE INVENTION

(25) The examples which follow illustrate the preparation of two control organic monolithic gels G0 and G0, of five organic monolithic gels according to the invention G1 to G5 and of the corresponding control porous carbons C0 and C0 and porous carbons according to the invention C1 to C5, with, as starting reagents: resorcinol (R) from Acros Organics, 98% pure, formaldehyde (F) from Acros Organics, 37% pure, a catalyst (C) consisting of hydrochloric acid for the gels G1 to G4 and of sodium carbonate for the gel G5, and poly(diallyldimethylammonium chloride) (P), 35% pure (in solution in water W), for the gels G1 to G5.

(26) These gels G0, G0 and G1 to G5 were prepared as follows.

(27) The resorcinol R and the polyelectrolyte P (with the exception of the gels G0 and G0) were, in a first step, dissolved in a container containing water. Then, after total dissolution, the formaldehyde F was added. The polymeric solution obtained was adjusted to the appropriate pH with the catalyst C, it being specified that all of these operations were carried out at ambient temperature (at approximately 22 C.). In a second step, the solution obtained was transferred into Teflon molds, which were then placed in an oven at 90 C. for 24 h in order to perform the gelation.

(28) The gel was then dried: in a humid chamber at 85 C. with a degree of humidity of 90% for 17 hours, so as to obtain the gels G0, G2, G4 and G5, or using supercritical CO.sub.2 after solvent exchange in a trifluoroacetic acid bath for 3 days and then in an absolute ethanol bath for 4 days, so as to obtain the aerogels G0, G1 and G3.

(29) Finally, the organic gels G0, G0 and G1 to G5 were pyrolyzed under nitrogen at a temperature of 800 C., in order to obtain the porous monolithic carbons C0, C0 and C1 to C5.

(30) In table 1 hereinafter: R/F is the molar ratio between resorcinol and formaldehyde, R/W is the mass ratio between resorcinol and water, denotes the mass fraction of polyelectrolyte, P/(R+F) is the mass ratio between the polyelectrolyte and the resorcinol-formaldehyde precursors, P/(R+F+W) is the mass ratio between the polyelectrolyte and the resorcinol-formaldehyde precursors supplemented with water, and CO.sub.2 sc denotes drying using supercritical CO.sub.2, as opposed to the oven-drying usable according to the invention.

(31) The thermal conductivity of the gels G0, G2 and G4 (see table 2) and of the porous carbons C0, C2 and C4 (see table 3) was measured at 22 C. with a Neotim conductivity meter according to the hot wire technique, and the mechanical properties in three-point compression and in tension of the gel G4 and of the corresponding porous carbon C4 were measured in comparison with those of a control silica aerogel G0 (see table 4) with an MTS tensile/compression testing machine according to standard ASTM C165-07.

(32) For each porous carbon C0, C0 and C1 to C5, the specific surface areas, the pore volumes and the average pore diameters were measured (table 2) using the Tristar 3020 instrument from Micromeritics.

(33) TABLE-US-00001 TABLE 1 Amounts of reagents/ process G0 G0 G1 G2 G3 G4 G5 R/F 0.5 0.5 0.5 0.5 0.5 0.5 0.5 R/W 0.03 0.03 0.03 0.03 0.03 0.03 0.20 P 0 0 0.4% 0.4% 0.4% 0.4% P/(R + F) 0 0 0.0626 0.0626 0.0640 0.0640 0.0379 P/(R + F + 0 0 0.0044 0.0044 0.0070 0.0070 0.0127 W) pH 3 3 3 3 1 1 6.13 Drying CO.sub.2 Oven CO.sub.2 Oven CO.sub.2 Oven Oven method sc sc sc

(34) TABLE-US-00002 TABLE 2 Organic gel G0 G0 G1 G2 G3 G4 G5 Density of the gel 0.40 1 0.20 0.40 0.04 0.04 0.20 Thermal 24 26 24 conductivity of the gel (mW/mK)

(35) TABLE-US-00003 TABLE 3 Porous carbon C0 C0 C1 C2 C3 C4 C5 Specific surface 983 18 1014 1080 769 1170 670 area of the carbon (m.sup.2/g) Pore volume (cm.sup.3/g) 0.58 0.012 0.87 0.95 0.32 0.47 0.26 of the carbon Average pore 3.6 10 10 5.4 4.1 3.9 diameter (nm) of the carbon Density of the 0.40 0.90 0.20 0.40 0.04 0.06 0.20 carbon Thermal conductivity 30 33 29 (mW/mK) of the carbon

(36) The comparison of the control porous carbons C0 and C0 with those of the invention C1 to C5 clearly shows that the addition of the cationic polyelectrolyte P makes it possible to maintain, for a low density obtained, a nanometric structure even with oven drying (see the specific surface area, pore volume and average pore diameter values of the porous carbons C2, C4 and C5 which are of the same order as those of C0), whereas, without this polyelectrolyte, the use of drying with supercritical CO.sub.2 is necessary in order to retain this nanostructure of the porous carbon C0.

(37) Under these conditions, the densities of the nanostructured gels G1 to G5 and carbons C1 to C5 according to the invention are always less than or equal to 0.4.

(38) If the pH is adjusted to 1, these results also show that it is possible to obtain a monolithic material (see gels G3 and G4 and carbons C3 and C4 of the invention) with much lower densities (less than or equal to 0.06).

(39) Finally, the results obtained for the gel G5 and the corresponding carbon C5 of the invention show that the synthesis can also be carried out in a less acidic and even slightly basic medium (pH>6).

(40) TABLE-US-00004 TABLE 4 Silica Structure of the aerogel* Porous gel or of the carbon G0 Gel G4 carbon C4 Density 0.1* 0.04 0.06 Compression modulus (MPa) 55* 800 1050 Breaking strength (MPa) 4* 25 20 *according to M. A. Aegerter et al., Aerogel Handbook Advances in Sol-Gel Derived Materials and Technologies, chap. 22.

(41) This table 4 shows that the gels and porous carbons according to the invention have mechanical properties which are very markedly improved in comparison with those of a known silica aerogel.