PREPARATION OF AN INSULATING COMPOSITE

Abstract

The invention relates to a binder composition for preparing a composite material, in particular for preparing an insulating material based on glass fibers or rock fibers. The invention also provides a method for preparing this composition as well as a method for preparing a composite material whose hygroscopicity is reduced.

Description

Title of the invention: PREPARATION OF AN INSULATING COMPOSITE

[0001] The invention relates to a binder composition for the preparation of a composite material, in particular for preparing an insulating material based on glass fibers or rock fibers. The invention also provides a method for preparing this composition as well as a method for preparing a composite material whose hygroscopicity is reduced.

[0002] Composite materials have long been used in many technical fields and therefore require significant development. In the field of construction, and in particular for thermal or sound insulation, many composite materials have been developed. Many of these composite materials consist of mineral fibers or particles treated using crosslinkable binder compositions.

[0003] Thus, these composite materials are generally prepared by crosslinking a composition applied to a mineral material in the form of fibers or particles. After crosslinking, the binder composition makes it possible to fix the material, in particular to confer its structuring or insulating properties to the final composite material. Improving the immobilization of air within the composite material makes it possible to obtain good insulating properties. Similarly, the effective fixing of the material by means of a crosslinked composition makes it possible to improve the structuring properties of the final composite material.

[0004] During their manufacture, their transport, their storage but especially once they have been implemented, these composite materials can be exposed to conditions which can be very different but also to conditions which can vary widely over time. Among the different conditions encountered by these composite materials throughout their life, humidity is not only very frequent, but is also particularly detrimental to these composite materials. When they are exposed to humidity for a prolonged period, these composite materials inevitably undergo a certain degree of aging which leads to the degradation of their properties. Unlike their intrinsic humidity level, the humidity level of the environment of these composite materials cannot always be easily controlled.Thus, one way to limit the exposure of these composite materials to humidity is to limit their intrinsic humidity level, both during their preparation and when they are implemented.

[0005] Even though fiberglass or rock fiber may be characterized by hygro- relatively moderate scopicity, composite materials prepared using crosslinkable binder compositions may have increased hygroscopicity which makes them particularly sensitive to surrounding humidity. Indeed, when they absorb moisture, these composite materials may undergo an alteration of their properties, in particular an alteration of their insulating properties or their mechanical properties. Furthermore, the absorption of moisture by these composite materials can also lead to health problems, in particular during the development of undesirable microorganisms.

[0006] Generally, these problems become more significant over time and particularly depending on the seasons due to variations in humidity levels encountered by composite materials.

[0007] A reduction, however minimal, in the moisture content of composite materials is therefore particularly useful. Indeed, these composite materials are generally used on a large scale and permanently fixed. They are often covered, making any intervention or treatment once they have been manufactured or after their installation very complex, if not impossible.

[0008] Thus, the reduction or elimination of the slightest source of humidity must be sought during the preparation of these composite materials, whether it is a direct source of humidity or an indirect source of humidity. Reducing the hygroscopicity of composite materials is therefore an essential goal during their manufacture. Indeed, these materials should have a reduced capacity to absorb the humidity present in their environment, in particular during their preparation or during their use.

[0009] Thus, it is important to reduce the quantities of mineral salts likely to be used or formed during the preparation of the crosslinkable binder compositions or likely to be used or formed during their implementation at the time of preparation of the composite material. Indeed, these mineral salts can lead to the presence of moisture within the crosslinkable binder composition or in the composite material resulting from the crosslinking of this composition. Limiting or banning these mineral salts can also make it possible to avoid the emission of harmful or odorous substances during their implementation, in particular during their crosslinking.

[0010] Furthermore, within the crosslinkable binder compositions used for the manufacture of composite materials, certain compounds should be avoided or eliminated, in particular for reasons of efficiency and safety but also for economic or environmental reasons. In particular, the aim is to eliminate urea-formaldehyde compounds and formaldehyde.

[0011] Crosslinking of these binder compositions involves ester or amide formation, is achieved by heating and may be catalyzed. Crosslinking catalysts Known effective crosslinking agents may include phosphorus, particularly phosphorus in oxidation states I, III or V. Reactions leading to crosslinking of the binder composition present on the material must be effectively controlled. Side reactions or inhibition of the reagents used must be avoided, as must antagonistic reactions. In particular, excessive moisture during ester or amide formation can disrupt or slow down crosslinking of the binder composition. Thus, during crosslinking, it is always useful to carefully control the kinetics of the ester or amide formation reaction.

[0012] It is therefore important to have improved means, in particular crosslinkable aqueous compositions or crosslinking agents, necessary for the manufacture of insulating composite materials. In particular, crosslinkable polymers can be applied to a material in the form of fibers or particles, in particular glass or rock. These polymers can also be used to produce coatings, in particular water-repellent coatings or mechanical, physicochemical or chemical protective coatings.

[0013] The manufacturing time of these composite materials is also an important factor. Improving the efficiency of the various reactions implemented, particularly during crosslinking, must therefore be sought.

[0014] There is therefore a need to have improved binder compositions for preparing composite materials which make it possible to provide solutions to all or part of the problems of the binder compositions of the state of the art.

[0015] Thus, the invention provides a binder composition R for preparing a composite material C comprising: A- at least one polymer A, non-sulfonated and non-phosphorus, of molecular mass Mw, measured by CES, ranging from 1,000 g / mol to 15,000 g / mol, prepared in water, at atmospheric pressure, by a polymerization reaction of at least one monomer M chosen from acrylic acid, methacrylic acid, a salt of acrylic acid, a salt of methacrylic acid, an oligomer of acrylic acid, an oligomer of methacrylic acid, a salt of an oligomer of acrylic acid, a salt of an oligomer of methacrylic acid and combinations thereof, in the presence of at least one initiator compound T and at least one metal compound Q chosen from a metal compound Q1 comprising iron, a metal compound Q2 comprising copper and combinations thereof; B- at least one polyfunctional compound B chosen from polyols, polyamines, aminoalcohols, (polyamino)alcohols, amino(polyalcohols), oses, osides and combinations thereof.

[0016] The polymer A according to the invention does not comprise any chemical residue comprising sulfur within the polymer chain and which originates from the reagents used during of its preparation. It is non-sulfonated. Similarly, polymer A according to the invention does not include any chemical residue comprising phosphorus within the polymer chain and which originates from the reagents used during its preparation. It is non-phosphorus.

[0017] The composition R according to the invention comprises the polymer A as an essential ingredient which can influence the pH of this composition. Thus, the pH of the composition R according to the invention can vary both during its preparation and during its implementation. In particular, the pH of the composition R can be lowered at the time of crosslinking of the composition R. Preferably, the binder composition R according to the invention has a pH of less than 8 or less than 7, preferably less than 6 or less than 4 or less than 3.5. More preferably, the pH of the binder composition R is less than 3 or less than 2.5.

[0018] The polymerization reaction carried out according to the invention is carried out in the absence of a chain transfer agent which comprises phosphorus or sulfur, in particular in the absence of such phosphorus- or sulfur-containing agents which are in the form of salts, in particular in the form of mineral salts. Similarly, the polymerization reaction carried out according to the invention is carried out in the absence of an initiator compound which comprises phosphorus or sulfur, in particular in the absence of such phosphorus- or sulfur-containing initiator compounds which are in the form of salts, in particular in the form of mineral salts.

[0019] In a particularly preferred manner according to the invention, polymer A is prepared in the absence of phosphite or hypophosphite, much more preferably in the absence of a compound comprising phosphorus.

[0020] Also particularly preferably according to the invention, polymer A is prepared in the absence of sulfite, di(hydrogen sulfite) or hydrogen sulfite, much more preferably, in the absence of chain transfer agent comprising sulfur.

[0021] Preferably according to the invention, the binder composition R comprises a quantity of mineral salts, preferably mineral salts resulting from the polymerization reaction, measured by ion chromatography, which is less than 2% by dry / dry weight relative to the quantity of monomers used. More preferably according to the invention, the binder composition R comprises a quantity of mineral salts, preferably mineral salts resulting from the polymerization reaction, measured by ion chromatography, which is less than 1% by dry / dry weight relative to the quantity of monomers used. More preferably according to the invention, the binder composition R comprises a quantity of mineral salts, preferably mineral salts resulting from the polymerization reaction, measured by ion chromatography, which is less than 0.5% by dry / dry weight or 0.3% by dry / dry weight dry / dry, relative to the quantity of monomers used.

[0022] Much more preferably according to the invention, the binder composition R comprises a zero quantity of mineral salt, preferably a zero quantity of mineral salt resulting from the polymerization reaction.

[0023] According to the invention, the quantities of mineral salts are determined by ion chromatography. A test sample of the aqueous dispersion resulting from the polymerization reaction comprising the polymer of approximately 80 mg is introduced into a 15 mL bottle. Mobile phase is added, up to a total mass of 15 g. The composition of the mobile phase is as follows: sodium carbonate: 0.009 mol / L. The ion chromatography chain for anion determination is composed of a “Dionex Aquion” type ion chromatography system with integrated degasser, the flow rate of which is set at 1 mL / min, containing a chemical suppressor, an AG9-HC precolumn, a CG3 metal trap precolumn, an NG1 precolumn and an AG9-HC column. Detection is carried out by means of a conductimetric detector. The ion chromatography device is calibrated with a series of sodium sulfate solution standards. The calibration range is between 0.5 and 100 ppm.The calibration curve is linear. Automatic dilution of the samples by the device allows to be in the calibration range. The acquisition and processing of the chromatogram are carried out using the “Chromeleon” 7.2.10 software.

[0024] According to the invention, the molecular mass Mw of the polymer A is less than 15,000 g / mol. Preferably according to the invention, polymer A has a weight-average molecular mass Mw, measured by CES, of less than 12,000 g / mol or less than 10,000 g / mol. More preferably, the weight-average molecular mass Mw, measured by CES, of polymer A is less than 8,000 g / mol or less than 6,000 g / mol, particularly less than 5,000 g / mol.

[0025] Also preferably according to the invention, the weight-average molecular mass Mw, measured by CES, of polymer A ranges from 1,200 g / mol to 12,000 g / mol or from 1,000 g / mol to 10,000 g / mol.

[0026] More preferably, according to the invention, the weight-average molecular mass Mw, measured by CES, of polymer A ranges from 1,500 g / mol to 8,000 g / mol or from 2,000 g / mol to 8,000 g / mol. Much more preferably, it ranges from 2,000 g / mol to 6,000 g / mol or from 2,500 g / mol to 6,000 g / mol.

[0027] Preferably according to the invention, polymer A has a polymolecularity index Ip, measured by CES, of less than 4 or ranging from 1.2 to 4. More preferably according to the invention, polymer A has a polymolecularity index Ip, measured by CES, ranging from 1.5 to 4; from 1.2 to 3 or from 1.5 to 3. Also more preferably according to the invention, polymer A has a polymolecularity index Ip, measured by CES, ranging from 1.2 to 2.5 or even from 1.5 to 2.5.

[0028] According to the invention, the molecular weight or mass Mw of polymer A and its polymolecularity index Ip are determined by Size Exclusion Chromatography (SEC). A test sample of the polymer solution corresponding to 90 mg of dry matter is introduced into a 10 mL flask. Mobile phase, containing 0.04% dimethylformamide (DMF), is added to a total mass of 10 g. The composition of this mobile phase is as follows: NaHCO3: 0.05 mol / L, NaNO3: 0.1 mol / L, triethanolamine: 0.02 mol / L, NaN3 0.03% by mass.The CES chain is composed of a "Waters" 510 isocratic pump, whose flow rate is set at 0.8 mL / min, a "Waters" 717+ sample changer, an oven containing a "Guard Column Ultrahydrogel Waters" precolumn of 6 cm length and 40 mm inner diameter, followed by a linear column of "Ultrahydrogel Waters" of 30 cm length and 7.8 mm inner diameter. Detection is ensured by means of a differential refractometer of "RI Waters" 410 type. The oven is brought to the temperature of 60°C and the refractometer is brought to the temperature of 45°C. The CES device is calibrated with a series of sodium polyacrylate standards supplied by "Polymer Standard Service" with peak molecular weights between 900 g / mol and 2,250,000 g / mol and polydispersity index between 1.4 and 1.7.The calibration curve is linear and takes into account the correction obtained using the flow marker: dimethylformamide (DMF). The acquisition and processing of the chromatogram are carried out using the software “PSS WinGPC Scientific” v 4.02. The chromatogram obtained is integrated into the area corresponding to molecular weights greater than 250 g / mol.

[0029] Preferably according to the invention, polymer A has a pH of less than 4 or less than 3.5. More preferably, the pH of polymer A is less than 3 or less than 2.5.

[0030] Preferably according to the invention, polymer A is prepared in water alone or in combination with a polar organic solvent, preferably a polar organic solvent chosen from primary alcohol, secondary alcohol and their combinations, more preferably isopropanol. In a particularly preferred manner according to the invention, polymer A is prepared in water alone.

[0031] Preferably for the binder composition R according to the invention, the polymer A is prepared by a polymerization reaction which is carried out at a temperature above 30°C and below 100°C, preferably below 90°C, more preferably below 80°C or 75°C.

[0032] According to the invention, polymer A may be non-neutralized or polymer A may be partially neutralized. Where appropriate, polymer A is preferably, by partially neutralized in the absence of mineral base or by means of an organic base or NH3.

[0033] When partially neutralized, polymer A may be neutralized by means of an ammonium salt or an amine, preferably an amine selected from triethanolamine, diethanolamine and combinations thereof.

[0034] Essentially for the invention, the preparation of the polymer A is carried out using the monomer M. Preferably for the binder composition R according to the invention, the monomer M is chosen from acrylic acid, methacrylic acid, an oligomer of acrylic acid, an oligomer of methacrylic acid and combinations thereof, preferably chosen from acrylic acid, methacrylic acid and combinations thereof, preferentially acrylic acid.

[0035] According to the invention, the monomer M can be combined with at least one other different monomer, preferably another monomer chosen from vinyl acetate, ethyl acrylate, methyl acrylate, hydroxyethylmethacrylate, hydroxyethylacrylate, hydroxypropylmethacrylate, hydroxypropylacrylate, maleic acid, maleic anhydride, itaconic acid and combinations thereof.

[0036] The polymer A according to the invention is prepared in water in the presence of at least one initiator compound T. Preferably according to the invention, the initiator compound T is chosen from peroxide, hydroperoxide and combinations thereof. More preferably according to the invention, the initiator compound T is chosen from hydrogen peroxide, tert-butyl hydroperoxide and combinations thereof. The preferred initiator compound T is hydrogen peroxide.

[0037] According to the invention, the initiator compound T may also be an organic compound, preferably an organic initiator compound T chosen from compounds with an azo group, preferably chosen from 4,4'-azobis(4-cyanovaleric) acid (CAS No. 2638-94-0), 2,2'-azobis(2-methylpropionamidine) dihydrochloride (CAS No. 2997-92-4), azo-bis-isobutyronitrile (AZDN or AIBN) and combinations thereof.

[0038] Essentially according to the invention, the polymer A is prepared in water in the presence of at least one metal compound Q. Preferably according to the invention, the compound Q is used in an amount by weight of metal ranging from 0.01% to 0.25%, preferably from 0.01% to 0.20% or from 0.01% to 0.15%, more preferably from 0.01% to 0.13%, relative to the amount by weight of monomers.

[0039] Also preferably, the metal compound Q is selected from copper salts (e.g. Cu1 or Cu11 salts), iron salts (e.g. Fe1 or Fe11 salts) and combinations thereof. More preferably, the metal compound Q is selected from organic copper anion salts, organic iron anion salts and combinations thereof.

[0040] In a particularly preferred manner, the metallic compound Q is chosen from copper carbonate, copper sulfate, iron carbonate, iron sulfate and combinations thereof.

[0041] Also particularly preferably, the metal compound Q1 comprises Fe1 or Fe11, preferably a salt of Fe1 or Fe11.

[0042] Also particularly preferably, the metal compound Q2 comprises Cu1 or Cu11, preferably a Cu1 or Cu11 salt.

[0043] In addition to polymer A, the binder composition R according to the invention comprises at least one polyfunctional compound B. Preferably according to the invention, compound B is chosen from glycerol, polyalkylene glycol (preferably polyethylene glycol, polypropylene glycol, polybutylene glycol), triethanolamine, ethanolamine, diethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, butanetriol, 1,4-butanediol, 1,6-hexanediol, pentaerythritol, sorbitol, 5-amino-1-pentanol, 2-(2-aminoethoxy)ethanol, N-(2-aminoethyl)ethanolamine, bis(N-hydroxyethyl)propane-1,3-diamine, diisopropa-nolamine, triisopropanolamine, N-methyldiethanolamine, N-butyldiethanolamine, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2,3-propanetriol, 1,2-butanediol, 1,4-butanediol, 2,3-butanediol, neopentyl glycol, trimethylolpropane, 1,2,4 butanetriol, 1,2-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 2,5-dimethyl-2,5-hexanediol, D-arabinose, L-arabinose, D-xylose, D-glucose,D-mannose, D-gallactose, D-glucosamine, D-fructose, maltose, sucrose, lactose, ethyl-nediamine, diethylenetriamine, triethylenetetramine, 1,3-propanediamine, 1,2-propanediamine, neopentyldiamine, hexamethylenediamine, octamethyl-nediamine, N-(2-aminoethyl)propane-1,3-diamine, 1,2,3-propanetriamine, N,N-bis(3-aminopropylamine) and combinations thereof. ,

[0044] More preferably according to the invention, compound B is chosen from glycerol, triethanolamine, trimethylolpropane, 1,2,4, butanetriol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, pentaerythritol, sorbitol and combinations thereof. Glycerol and triethanolamine are particularly preferred.

[0045] Preferably according to the invention, compound B has a molecular mass ranging from 50 g / mol to 1000 g / mol, preferably from 55 g / mol to 500 g / mol or from 55 g / mol to 250 g / mol.

[0046] Essentially according to the invention, ingredients A and B can react with each other during the crosslinking of the binder composition R, in particular by reaction of the functional groups of compound B with the carboxylic groups of polymer A. Preferably according to the invention, the binder composition R comprises a molar quantity of functional groups of compound B ranging from 5% to 100%, preferably from 10% to 100% or from 10% to 90% or from 20% to 100% or from 20% to 80%, relative to the total molar quantity of carboxylic groups of polymer A.

[0047] In addition to ingredients A and B, the binder composition R according to the invention may also comprise at least one compound chosen from a compound comprising phosphorus in oxidation state I, a compound comprising phosphorus in oxidation state III, a compound comprising phosphorus in oxidation state V and combinations thereof. The binder composition R according to the invention may therefore also comprise at least one compound chosen from phosphorous acid, a compound comprising phosphite, a compound comprising hypophosphite and combinations thereof, preferably a compound chosen from phosphorous acid, sodium phosphite, ammonium phosphite, sodium hypophosphite, ammonium hypophosphite and combinations thereof.

[0048] The composition R according to the invention may also comprise at least one compound chosen from 2-sulfoacetic acid, methanesulfonic acid, para-toluenesulfonic acid (PTSA), sulfuric acid, their salts and their combinations. It may also comprise at least one other substance chosen from a thickening agent, an anti-foaming agent, a neutralizing agent, a buffering agent, a preservative, inert fillers (such as aluminosilicates, quartz, precipitated or pyrogenic silica, light or heavy spar, talc or dolomite), pigments (such as titanium white, zinc white or iron oxide black), an adhesion promoting agent, a flame retardant and their combinations.

[0049] In a particularly advantageous manner according to the invention, the binder composition R does not comprise a urea-formaldehyde compound or formaldehyde. It may also not comprise a compound comprising phosphorus in oxidation state I or a compound comprising phosphorus in oxidation state III or not comprise a compound comprising phosphorus in oxidation state V.

[0050] Advantageously, the invention also provides a simple method for preparing a binder composition R for preparing a composite material C according to the invention.

[0051] The method for preparing the binder composition R according to the invention comprises mixing: - at least one polymer A, non-sulfonated and non-phosphorus, of molecular mass Mw, measured by CES, ranging from 1,000 g / mol to 10,000 g / mol, prepared in water, at atmospheric pressure, by a polymerization reaction of at least one monomer M chosen from acrylic acid, methacrylic acid, a salt of acrylic acid, a salt of methacrylic acid, an oligomer of acrylic acid, an oligomer of methacrylic acid, a salt of an oligomer of acrylic acid, a salt of an oligomer of methacrylic acid and combinations thereof, in the presence of at least one initiator compound T and at least one metal compound Q chosen from a metal compound Q1 comprising iron, a metal compound Q2 comprising copper and their com- combinations; with: - at least one polyfunctional compound B chosen from polyols, polyamines, amino alcohols, (polyamino) alcohols, amino (poly alcohols), oses, osides and combinations thereof.

[0052] Very advantageously according to the invention, the mixing of the polyfunctional compound B with the polymer A, and the possible other ingredients of the binder composition R, is carried out by means of conventional techniques and devices.

[0053] The binder composition R according to the invention is particularly useful and effective for preparing a composite material. Thus, the invention also provides a method for preparing a composite material C comprising: - the application to a material F chosen from woven heat-resistant substrates, non-woven heat-resistant substrates and their combinations, of at least one binder composition R according to the invention; then - crosslinking of the impregnated material F using the binding composition R.

[0054] The crosslinking of the impregnated material F results from the crosslinking of the binder composition R by reaction between the polymer A and the polyfunctional compound B. Very advantageously according to the invention, the application and crosslinking of the binder composition R on the material F are carried out using conventional techniques and devices.

[0055] Preferably according to the invention, during this preparation method, at least one of the steps of applying the binder composition R to the material F or of crosslinking the binder composition R to the material F is carried out at a pH of less than 5. More preferably, at least one of the steps of applying or crosslinking the binder composition R is carried out at a pH of less than 4 or less than 3.5.

[0056] Also preferably, at least one of the steps of applying the binder composition R to the material F or of crosslinking the binder composition R to the material F is carried out at a temperature ranging from 100°C to 250°C, more preferably at a temperature ranging from 150°C to 240°C or from 170°C to 230°C.

[0057] The application of the binder composition R is essential for this preparation method. Advantageously, other compounds or substances can also be applied to the material F. Then, it is also possible to use at least one compound chosen from 2-sulfoacetic acid, methanesulfonic acid, para-toluenesulfonic acid (PTSA), sulfuric acid, their salts and their combinations.

[0058] In this case, the binder composition R may also comprise at least one compound chosen from 2-sulfoacetic acid, methanesulfonic acid, para-toluenesulfonic acid (PTSA), sulfuric acid, their salts and their combinations.

[0059] Very preferably, this method of preparing a composite material C is carried out in the absence of urea-formaldehyde compound or formaldehyde compound. In this case, the binder composition R does not comprise urea-formaldehyde compound or formaldehyde compound.

[0060] Preferably, the method for preparing a composite material C according to the invention may also use at least one compound chosen from a compound comprising phosphorus in oxidation state I, a compound comprising phosphorus in oxidation state III, a compound comprising phosphorus in oxidation state V and combinations thereof. Then, the binder composition R may also comprise at least one compound chosen from a compound comprising phosphorus in oxidation state I, a compound comprising phosphorus in oxidation state III, a compound comprising phosphorus in oxidation state V and combinations thereof. Preferred phosphorus compounds comprise phosphite or hypophosphite, in particular sodium hypophosphite or ammonium hypophosphite.

[0061] In certain cases, the method for preparing a composite material C according to the invention may also be carried out in the absence of a compound chosen from a compound comprising phosphorus in oxidation state I, a compound comprising phosphorus in oxidation state III, a compound comprising phosphorus in oxidation state V and combinations thereof. Then, the binder composition R does not comprise any compound chosen from a compound comprising phosphorus in oxidation state I, a compound comprising phosphorus in oxidation state III, a compound comprising phosphorus in oxidation state V and combinations thereof.

[0062] For the method of preparing a composite material C according to the invention, the material F is preferably in the form of heat-resistant particles or in the form of heat-resistant fibers.

[0063] Preferably, the material F is chosen from aramid fibers, ceramic fibers, non-graphite carbon fibers, polyimide fibers, rock wool, slag fibers, glass fibers and combinations thereof. Rock wool, slag fibers and glass fibers are particularly preferred.

[0064] Also preferably, the composite material C is an insulating material.

[0065] The preparation method according to the invention is particularly effective for obtaining a composite material C having advantageous properties. Preferably according to the invention, the composite material C comprises a quantity of mineral salts, preferably mineral salts resulting from the polymerization reaction, less than 2% dry / dry weight or 1% dry / dry weight, preferably less than 0.5% dry / dry weight or 0.3% dry / dry weight, relative to the quantity of monomers. According to the invention, the composite material C may comprise a quantity no mineral salts.

[0066] More preferably according to the invention, the composite material C comprises a zero quantity of mineral salt, much more preferably a zero quantity of mineral salt resulting from the polymerization reaction.

[0067] The mineral salts resulting from the polymerization reaction may come from a possible chain transfer agent or from the initiator compound.

[0068] Preferably according to the invention, the crosslinked composite material C comprises less than 0.5% by weight, more preferably less than 0.4% by weight or less than 0.2% by weight, of moisture relative to the total quantity of composite material C.

[0069] According to the invention, the moisture content of composite material C obtained according to the invention is measured by taking a sample of material C obtained according to the invention (for example 10 g) which is heated at 150°C in an oven until its mass is constant for 20 minutes. The loss of mass is determined by gravimetry and is expressed in % by weight from the initial mass of the sample. This variation in mass makes it possible to determine the moisture content of the sample.

[0070] Thus, the preparation method according to the invention makes it possible to obtain a composite material C which has particularly useful properties. The invention then also provides a composite material C prepared according to the method according to the invention. Preferably according to the invention, the composite material C comprises: - from 80% dry weight to 99% dry weight of material F and - from 1% by dry weight to 20% by dry weight of crosslinked binder composition R.

[0071] In a novel manner, the invention provides a polymer A which makes it possible to prepare a composite material C according to a method during which the carboxylic groups of this polymer can react effectively with the functional groups of compound B, in particular by condensation. Polymer A therefore has properties useful for these condensation reactions.

[0072] The invention therefore also provides a condensation agent for at least one compound B chosen from polyols, polyamines, amino alcohols, (polyamino) alcohols, amino (polyalcohols), oses, osides and combinations thereof, comprising at least one polymer A according to the invention.

[0073] Thanks to the polymer A used according to the invention, it is therefore possible to prepare a composite material C having improved properties, in particular a composite material C whose sensitivity to humidity is reduced. The invention therefore provides a method for reducing the hygroscopicity, measured by weighing, of a composite material C comprising at least one composite material F, chosen from woven heat-resistant substrates, non-woven heat-resistant substrates, on which is applied and then crosslinked according to the preparation method according to the invention, at least one combination of at least one polymer A and at least one compound B according to the invention, compared to a comparative composite material Cp comprising the same composite material F, on which is applied and then crosslinked according to the preparation method according to the invention, at least one combination of at least one comparative polymer Ap different from polymer A and at least one compound B according to the invention, in the absence of polymer A.

[0074] Preferably, the method according to the invention for reducing the hygroscopicity, measured by weighing, of a composite material C comprising at least one composite material F, chosen from woven heat-resistant substrates, non-woven heat-resistant substrates, on which is applied and then crosslinked according to the preparation method according to the invention, at least one combination of at least one binder composition R according to the invention, compared to a comparative composite material Cp comprising the same composite material F, on which is applied and then crosslinked according to the preparation method according to the invention, at least one combination of at least one comparative composition Rp according to the invention which does not comprise polymer A and which comprises at least one comparative polymer Ap different from polymer A.

[0075] According to the invention, the particular, advantageous or preferred characteristics of the binder composition R define composite materials C, condensation agents according to the invention as well as methods for their preparation or methods which implement them which are also particular, advantageous or preferred.

[0076] The following examples illustrate the various aspects of the invention. EXAMPLES

[0077] Preparation of a composition RI according to the invention comprising the polymer Al and the polyfunctional compound B1

[0078] 1.449 g of copper sulfate pentahydrate (compound Q2), 0.698 g of iron sulfate heptahydrate (compound Ql) and 450 g of water are introduced into a glass reactor. The reactor is heated to 97°C + / - 2°C.

[0079] In a first beaker, 531.4 g of monomer M (acrylic acid) are weighed. In a second beaker, 70 g of initiator compound T (hydrogen peroxide in aqueous solution at 35% by mass) and 81 g of water are weighed.

[0080] The reagents from the 2 beakers are introduced in parallel into the reactor for 2 hours for the first and 2 hours and 15 minutes for the second and the temperature is maintained at 97°C + / - 2°C. Then, the medium is allowed to cool to room temperature. An aqueous composition is obtained comprising the copolymer Al according to the invention at 44.2% by weight of dry extract, the composition, the quantities of salts and the characteristics of which are detailed in Table 1.

[0081] Then, 214 g of an 85% by weight solution in water of triethanolamine (compound Bl) are added with stirring to obtain the composition RI according to the invention.

[0082] Preparation of a composition R2 according to the invention comprising the polymer A2 and the polyfunctional compound B2

[0083] 1.23 g of copper sulfate pentahydrate (compound Q2), 0.59 g of iron sulfate heptahydrate (compound Q1) and 450 g of water are introduced into a glass reactor. The reactor is heated to 97°C + / - 2°C.

[0084] In a first beaker, 531.4 g of monomer M (acrylic acid) are weighed. In a second beaker, 59 g of initiator compound T (hydrogen peroxide in aqueous solution at 35% by mass) and 81 g of water are weighed.

[0085] The reagents from the 2 beakers are introduced in parallel into the reactor for 2 hours for the first and 2 hours and 15 minutes for the second and the temperature is maintained at 97°C + / - 2°C. Then, the medium is allowed to cool to room temperature. An aqueous composition is obtained comprising the copolymer A2 according to the invention at 45.25% by weight of dry extract, the composition, the quantities of salts and the characteristics of which are detailed in Table 1. Then, 174 g of glycerol (compound B2) are added with stirring to obtain the composition R2 according to the invention.

[0086] [tab 1] Polymer Mw (g / mol) IP Cu (wt%) Fe (wt%) SO42-wt%) Al 3900 2.1 0.07 0.03 0.15 A2 4500 7 9: 0.06 0.03 0.13

[0087] The binder compositions RI and R2 according to the invention comprise very small quantities of mineral salts, thus limiting their sensitivity to water but also the sensitivity to water of the composite material C resulting from the application to a material F of these compositions RI and R2 followed by the crosslinking of the impregnated material F.

Claims

Claims

1. Binder composition R for preparing a composite material C comprising: A- at least one polymer A, non-sulfonated and non-phosphorus, of molecular mass Mw, measured by CES, ranging from 1,000 g / mol to 15,000 g / mol, prepared in water, at atmospheric pressure, by a polymerization reaction of at least one monomer M chosen from acrylic acid, methacrylic acid, an acrylic acid salt, a methacrylic acid salt, an acrylic acid oligomer, a methacrylic acid oligomer, a salt of an acrylic acid oligomer, a salt of a methacrylic acid oligomer and combinations thereof, in the presence of at least one initiator compound T and at least one metal compound Q chosen from a metal compound Q1 comprising iron, a metal compound Q2 comprising copper and combinations thereof;B- at least one polyfunctional compound B chosen from polyols, polyamines, aminoalcohols, (polyamino)alcohols, amino(polyalcohols), oses, osides and combinations thereof.;

2. Binder composition R according to claim 1: - having a pH of less than 8 or less than 7, preferably less than 6 or less than 4 or less than 3.5, preferably less than 3 or less than 2.5; or - comprising an amount of mineral salts, preferably mineral salts resulting from the polymerization reaction, measured by ion chromatography, of less than 2% dry / dry weight or less than 1% dry / dry weight, preferably less than 0.5% dry / dry weight or 0.3% dry / dry weight, relative to the amount of monomers used, preferably a zero amount of mineral salt, preferably a zero amount of mineral salt resulting from the polymerization reaction.

3. Binder composition R according to one of claims 1 or 2 for which: - the polymer A has a weight-average molecular mass Mw, measured by CES, of less than 12,000 g / mol or less than 10,000 g / mol, preferably less than 8,000 g / mol or less than 6,000 g / mol, particularly less than 5,000 g / mol; or - the polymer A has a weight-average molecular mass Mw, measured by CES, ranging from 1,200 g / mol to 12,000 g / mol or

4. 1,000 g / mol to 10,000 g / mol, preferably ranging from 1,500 g / mol to 8,000 g / mol or from 2,000 g / mol to 8,000 g / mol, more preferably ranging from 2,000 g / mol to 6,000 g / mol or from 2,500 g / mol to 6,000 g / mol; Or - polymer A has a polymolecularity index Ip, measured by CES, of less than 4 or ranging from 1.2 to 4 or from 1.5 to 4; from 1.2 to 3 or from 1.5 to 3; from 1.2 to 2.5 or even from 1.5 to 2.5; or - polymer A has a pH of less than 4 or less than 3.5, preferably less than 3 or less than 2.5; or - polymer A is prepared in the absence of phosphite or hypophosphite, preferably in the absence of a compound comprising phosphorus; or - polymer A is prepared in the absence of sulfite, di(hydrogen sulfite) or hydrogen sulfite, preferably in the absence of a chain transfer agent comprising sulfur; or - polymer A is prepared in water alone or in combination with a polar organic solvent, preferably a polar organic solvent chosen from primary alcohol, secondary alcohol and their combinations, more preferably isopropanol; or - polymer A is non-neutralized or polymer A is partially neutralized, preferably partially neutralized in the absence of a mineral base or by means of an organic base or NH3, preferably by means of an ammonium salt or an amine, preferably an amine chosen from triethanolamine, diethanolamine and combinations thereof. Binder composition R according to one of claims 1 to 3 for which: - the monomer M is chosen from acrylic acid, methacrylic acid, an oligomer of acrylic acid, an oligomer of methacrylic acid and their combinations; preferably chosen from acrylic acid, methacrylic acid and their combinations; preferentially acrylic acid; or - the monomer M is combined with at least one other different monomer chosen from vinyl acetate, ethyl acrylate, methyl acrylate, hydroxyethylmethacrylate, hydroxyethylacrylate, hydroxypropylmethacrylate, hydroxypropylacrylate, maleic acid, maleic anhydride, itaconic acid and combinations thereof; or - the initiator compound T is chosen from peroxide, hydroperoxide and their combinations, preferably hydrogen peroxide, hydro tert-butyl peroxide and combinations thereof, preferably hydrogen peroxide; or - the initiator compound T is an organic compound, preferably an organic initiator compound T chosen from compounds with an azo group, preferably chosen from 4,4'-azobis(4-cyanovaleric) acid (CAS No. 2638-94-0), 2,2'-azobis(2-methylpropionamidine) dihydrochloride (CAS No. 2997-92-4), azo-bis-isobutyronitrile (AZDN or AIBN) and combinations thereof; or - the metal compound Q is used in an amount by weight of metal ranging from 0.01% by weight to 0.25% by weight or from 0.01% by weight to 0.20% by weight, preferably from 0.01% to 0.15%, more preferably from 0.01% by weight to 0.13% by weight, relative to the amount by weight of monomers; or - the metallic compound Q is chosen from copper salts (for example Cu1 or Cu11 salts), iron salts (for example Fe1 or Fe11 salts) and combinations thereof, preferably salts of organic copper anions, salts of organic iron anions and combinations thereof; or -the metallic compound Q is selected from copper carbonate, copper sulfate, iron carbonate, iron sulfate and combinations thereof; or - the metallic compound Q1 comprises Fe1 or Fe11, preferably a salt of Fe1 or Fe11, or the metallic compound Q2 comprises Cu1 or Cu11, preferably a salt of Cu1 or Cu11.

5. Binder composition R according to one of claims 1 to 4 for which the polymerization reaction is carried out at a temperature above 30°C and below 100°C, preferably below 90°C, more preferably below 80°C or 75°C.

6. Binder composition R according to one of claims 1 to 5 for which: - compound B is chosen from glycerol, polyalkylene glycol (preferably polyethylene glycol, polypropylene glycol, polybutylene glycol), triethanolamine, ethanolamine, diethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, butanetriol, 1,4-butanediol, 1,6-hexanediol, pentaerythritol, sorbitol, 5-amino-1-pentanol, 2-(2-aminoethoxy)ethanol, N-(2-aminoethyl)ethanolamine, bis(N-hydroxyethyl)propane-1,3-diamine, diisopropanolamine, triisopropanolamine, N-methyldiethanolamine, N-butyldiethanolamine, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2,3-propanetriol, 1,2-butanediol, 1,4-butanediol, 2,3-butanediol, neopentyl glycol, trimethylolpropane, 1,2,4 butanetriol, 1,2-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 2,5-dimethyl-2,5-hexanediol, D-arabinose, L-arabinose, D-xylose, D-glucose, D-mannose, D-gallactose, D-glucosamine, D-fructose, maltose, sucrose, lactose, ethylenediamine, diethylenetriamine, triethylene-tetramine, 1,3-propanediamine, 1,2-propanediamine, neopentyldiamine, hexamethylenediamine, octamethylenediamine, N-(2-aminoethyl)propane-1,3-diamine, 1,2,3-propanetriamine, N,N-bis(3-aminopropylamine) and combinations thereof; - preferably compound B is chosen from glycerol, triethanolamine, trimethylolpropane, 1,2,4, butanetriol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, pentaerythritol, sorbitol and combinations thereof; or - compound B has a molecular mass ranging from 50 g / mol to 1000 g / mol, preferably from 55 g / mol to 500 g / mol or from 55 g / mol to 250 g / mol;or - which comprises a molar quantity of functional groups of compound B ranging from 5% to 100%, preferably from 10% to 100% or from 10% to 90% or from 20% to 100% or from 20% to 80%, relative to the total molar quantity of carboxylic groups of polymer A.;

7. Binder composition R according to one of claims 1 to 6 also comprising: - at least one compound chosen from a compound comprising phosphorus in oxidation state I, a compound comprising phosphorus in oxidation state III, a compound comprising phosphorus in oxidation state V and combinations thereof; or - at least one compound chosen from 2-sulfoacetic acid, methanesulfonic acid, para-toluenesulfonic acid (PTSA), sulfuric acid, their salts and combinations thereof.

8. Binder composition R according to one of claims 1 to 6 not comprising a urea-formaldehyde compound or formaldehyde; or not comprising a compound comprising phosphorus in oxidation state I or a compound comprising phosphorus in oxidation state III or not comprising a compound comprising phosphorus in oxidation state V.

9. Method for preparing a binder composition R for preparing a composite material C according to one of claims 1 to 8 comprising mixing: - at least one polymer A, non-sulfonated and non-phosphorus, of molecular mass Mw, measured by CES, ranging from 1,000 g / mol to 10,000 g / mol, prepared in water, at atmospheric pressure, by a polymerization reaction of at least one monomer M chosen from acrylic acid, methacrylic acid, a salt of acrylic acid, a salt of methacrylic acid, an oligomer of acrylic acid, an oligomer of methacrylic acid, a salt of an oligomer of acrylic acid, a salt of an oligomer of methacrylic acid and combinations thereof, in the presence of at least one initiator compound T and at least one metal compound Q chosen from a metal compound Q1 comprising iron, a metal compound Q2 comprising copper and combinations thereof; with: - at least one polyfunctional compound B chosen from polyols, polyamines, amino alcohols, (polyamino) alcohols, amino (poly alcohols), oses, osides and their combinations.

10. A method of preparing a composite material C comprising: - the application to a material F chosen from woven heat-resistant substrates, non-woven heat-resistant substrates and their combinations, of at least one binder composition R according to one of claims 1 to 8; then - crosslinking of the impregnated material F using the binding composition R.

11. A method of preparation according to claim 10 wherein: - at least one of the steps of applying the binder composition R to the material F or of crosslinking the binder composition R to the material F is carried out at a pH of less than 5, preferably at a pH of less than 4 or less than 3.5; or for which: - at least one of the steps of applying the binder composition R to the material F or of crosslinking the binder composition R to the material F is carried out at a temperature ranging from 100°C to 250°C, preferably from 150°C to 240°C or from 170°C to 230°C; or for which: - at least one compound chosen from 2-sulfoacetic acid, methanesulfonic acid, para-toluenesulfonic acid (PTSA), sulfuric acid, their salts and their combinations is also used; or for which: - the binding composition R also comprises at least one compound chosen from 2-sulfoacetic acid, methanesulfonic acid, para-toluenesulfonic acid (PTSA), sulfuric acid, their salts and their combinations; or - which is implemented in the absence of urea-formaldehyde compound or formaldehyde compound; or for which: - the binder composition R does not comprise urea-formaldehyde compound or formaldehyde compound.

12. Preparation method according to one of claims 10 or 11: - also using at least one compound chosen from a compound comprising phosphorus in oxidation state I, a compound comprising phosphorus in oxidation state III, a compound comprising phosphorus in oxidation state V and combinations thereof; or for which: - the binder composition R also comprises at least one compound chosen from a compound comprising phosphorus in oxidation state I, a compound comprising phosphorus in oxidation state III, a compound comprising phosphorus in oxidation state V and combinations thereof.

13. Preparation method according to one of claims 10 or 11: - also carried out in the absence of a compound chosen from a compound comprising phosphorus in oxidation state I, a compound comprising phosphorus in oxidation state III, a compound comprising phosphorus in oxidation state V and combinations thereof; or for which: - the binder composition R does not comprise any compound chosen from a compound comprising phosphorus in oxidation state I, a compound comprising phosphorus in oxidation state III, a compound comprising phosphorus in oxidation state V and combinations thereof.

14. Method according to one of claims 10 to 13 for which: - the material F is in the form of heat-resistant particles or in the form of heat-resistant fibers; or - the material F is chosen from aramid fibers, ceramic fibers, non-graphite carbon fibers, polyimide fibers, rock wool, slag fibers, glass fibers and combinations thereof; or - the composite material C is an insulating material; or - the composite material C comprises a quantity of mineral salts, preferably mineral salts resulting from the polymerization reaction, of less than 2% dry / dry weight or 1% dry / dry weight, preferably less than 0.5% dry / dry weight or 0.3% dry / dry weight, by relative to the amount of monomers, preferably a zero amount of mineral salt, preferably a zero amount of mineral salt resulting from the polymerization reaction; or - the crosslinked composite material C comprises less than 0.5% by weight, preferably less than 0.4% by weight or less than 0.2% by weight, of moisture relative to the total amount of composite material C.

15. Composite material C prepared according to the method defined by one of claims 10 to 14; preferably composite material C comprising: - from 80% by dry weight to 99% by dry weight of material F and - from 1% by dry weight to 20% by dry weight of crosslinked binder composition R.

16. Condensing agent for at least one compound B chosen from polyols, polyamines, aminoalcohols, (polyamino)alcohols, amino(polyalcohols), oses, osides and combinations thereof, comprising at least one polymer A according to one of claims 1 to A

17. U. Method for reducing the hygroscopicity, measured by weighing, of a composite material C comprising at least one composite material F, chosen from woven heat-resistant substrates, non-woven heat-resistant substrates, on which is applied and then crosslinked according to the preparation method according to one of claims 10 to 14, at least one combination of at least one polymer A and at least one compound B according to claims 1 to 8, preferably at least one binder composition R according to one of claims 1 to 8, compared to a comparative composite material Cp comprising the same composite material F, on which is applied and then crosslinked according to the preparation method according to one of claims 10 to 14, at least one combination of at least one comparative polymer Ap different from polymer A and at least one compound B according to claims 1 to 8 and in the absence of polymer A,preferably at least one comparative composition Rp according to one of claims 1 to 8 which does not comprise polymer A and which comprises at least one comparative polymer Ap different from polymer A.,