Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
  • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
  • C03C25/10—Coating
  • C03C25/1025—Coating to obtain fibres used for reinforcing cement-based products
  • C03C25/103—Organic coatings
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
  • C03C25/10—Coating
  • C03C25/24—Coatings containing organic materials
  • C03C25/26—Macromolecular compounds or prepolymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
  • C08G18/6492—Lignin containing materials; Wood resins; Wood tars; Derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
  • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
  • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/045—Reinforcing macromolecular compounds with loose or coherent fibrous material with vegetable or animal fibrous material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
  • C08K7/04—Fibres or whiskers inorganic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
  • C08K7/04—Fibres or whiskers inorganic
  • C08K7/14—Glass
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L97/00—Compositions of lignin-containing materials
  • C08L97/005—Lignin
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J197/00—Adhesives based on lignin-containing materials
  • C09J197/005—Lignin

Definitions

• thermosetting binder composition based on water-soluble or dispersible lignin ester for binding fibers
• the present invention relates to a process for preparing a thermosetting binder composition based on water-soluble or dispersible ester lignin obtained by reaction between a lignin, in the presence of an organic monocarboxylic or sulfonic acid, with an organic polycarboxylic acid. non-polymeric, as well as the thermosetting binder composition obtained by such a process.
• thermosetting binder composition also relates to the use of such a thermosetting binder composition in a process for manufacturing an insulation product.
• Said thermosetting binder composition after dilution in water, forms an aqueous sizing composition, making it possible to bond together both natural organic fibers and mineral fibers (after hardening of this sizing composition on the fibers) , for the manufacture of insulating products.
• These insulating products obtained by said process are usually used for the production of low density wood fiber panels (density less than 250 kg/m 3 ) and mineral fiber panels with a density less than 120 kg/m 3 .
• thermosetting binders to bind mineral fibers, in particular mineral wools.
• thermoset polyesters by reacting together reducing sugars and/or non-reducing sugars and/or hydrogenated sugars, carrying hydroxyl groups, with polycarboxylic acids in the presence of a catalyst, generally sodium hypophosphite (WO 2009/080938, WO 2010/029266, WO 2013/014399, WO 2013/021112).
• a catalyst generally sodium hypophosphite
• these sugar-based binders require a very high temperature, generally between 180°C and 210°C, to form over a time generally less than 30 min; this is why they have proven to be poorly suited to bonding natural organic fibers, because said organic fibers are then degraded (or even burned) at such temperatures.
• the sizing compositions described in the aforementioned documents are diluted aqueous solutions, not very viscous and monomeric reagents of low molar masses, less than 500 g. mol -1 . They are generally sprayed on the mineral fibers, while still hot, immediately after their formation. Immediately after application of the sizing composition to the fibers, evaporation of the aqueous phase begins. When the fibers are collected and assembled in the form of a mat on the collecting belt, they are sticky and the film of sizing composition which envelops the mineral fibers still contains water.
• Heating the bonded fiber mat at high temperatures for a few minutes then results in the hardening (or crosslinking) of the reactive system and the formation of a water-insoluble organic binder, and consequently the desired insulating product.
• This last step therefore requires high temperatures, thus requiring a large quantity of energy, to manufacture the desired insulating products.
• resols are obtained by condensation of phenol and formaldehyde, in the presence of a basic catalyst.
• these resols contain a certain proportion of unreacted monomers, in particular formaldehyde, the presence of which is not desired because of its proven harmful effects.
• resole resins are generally treated with urea which reacts with free formaldehyde trapping it as non-volatile urea-formaldehyde condensates.
• urea in the resin also provides a certain economic advantage due to its low cost, because it can be introduced in relatively large quantities without affecting the usability of the resin, in particular without harming the mechanical performance of the resin. final product, which significantly lowers the total cost of the resin.
• the urea-formaldehyde condensates are not stable. They decompose by giving back formaldehyde and urea, in turn degraded at least partially into ammonia, which are released into the atmosphere of the factory and must then be subject to capture procedures to reduce their impact on the environment.
• binders obtained after hardening or crosslinking of sizing compositions comprising polyisocyanates are known to use binders obtained after hardening or crosslinking of sizing compositions comprising polyisocyanates.
• polyisocyanates most commonly used in the wood fiber industry, we can cite poly(methylene diphenyl isocyanate) (pMDI, CAS number 9016-87-9) which is a technical grade mixture containing 30 to 80% of MDI (methylene diphenyl isocyanate) and higher molecular weight homologs of formula: [Formula 1]
• EMDI emusifiable pMDIs
• EP0516361 emusifiable pMDIs
• pMDI and a small percentage of pMDI functionalized with hydrophilic chains, for example polyethoxylated chains making it possible to stabilize the emulsion.
• the use of pMDI in the form of aqueous emulsions allows regular distribution of the binder on natural organic fibers without prior drying, which constitutes a significant energy saving.
• binders based on polyisocyanates even in the form of aqueous emulsions of pMDI, constitutes a significant harmful problem at the place of manufacture of insulating products, due to the presence of polyisocyanates.
• polyisocyanates remain expensive raw materials and are very reactive.
• sizing compositions based on polyisocyanates can harden before shaping and heating the insulating product, which leads to tedious cleaning of the equipment and, above all, the cessation of production.
• the present invention is based on the discovery that it was possible:
• thermosetting binder composition not very harmful, inexpensive, stable but sufficiently reactive, so that it can be used (after dilution in water) to bind both mineral fibers and fibers natural organic compounds, and thus manufacture insulating products with good mechanical properties
• thermosetting binder composition comprising the following steps:
• thermosetting binder composition and “sizing composition” are not synonyms.
• the term “thermosetting binder composition” designates concentrated aqueous solutions or dispersions, that is to say with a high solids or dry matter content (several tens of percent). These compositions can be stored and transported. They are fluid enough to be pumped, but too viscous to be sprayed as is onto the fibers.
• the term “sizing composition” refers to considerably less concentrated aqueous solutions or dispersions having a solids content of less than 20% by weight. They are generally obtained by diluting thermosetting binder compositions with water.
• organic binder means an insoluble binder obtained by hardening (or crosslinking) of the aqueous sizing composition previously applied to the fibers, during the heating step of the assembly of said fibers.
• the process according to the invention made it possible to obtain a pre-polymerized binder composition comprising at least one lignin ester that is stable and soluble or dispersible in water at room temperature.
• Said binder composition comprising at least one ester lignin can in fact form pumpable and infinitely dilutable aqueous solutions or dispersions, which can then be used as aqueous sizing compositions to bind both mineral fibers and natural organic fibers.
• These aqueous solutions or dispersions can have viscosities perfectly compatible with a conventional sizing system for different types of fibers by spraying using nozzles for example (such as a spray crown) or by impregnation.
• the term “soluble in water” means an ester lignin which is dissolved up to 30% by weight in water and the term “dispersible in water” means an ester lignin whose particles are dispersed up to 30% in water, without precipitation.
• the term “pre-polymerized” or “prepolymerization” means an esterification reaction between a part of the aliphatic hydroxyl groups of the lignin and a part of the carboxyl groups of the non-polymeric polycarboxylic acid(s). (s) and between a part of the hydroxyl groups of the lignin and a part of the carboxyl groups of the lignin itself leading to the formation of the ester lignin.
• the mixture in the process for preparing a thermosetting binder composition according to the invention, comprises at least one lignin.
• the lignin according to the invention is a lignin extracted from so-called “native” lignin which is a biomolecule forming part of a family of polyphenolic polymer macromolecules (tannin family lato sensu), which is one of the main components of wood with cellulose. and hemicellulose.
• Native lignin is a macromolecule with a molar mass well above 10,000 g. mol' 1 and which is not soluble in water. Native lignin is present mainly in vascular plants and in some algae. Its main functions are to provide rigidity, impermeability to water and great resistance to decomposition.
• vascular plants, woody and herbaceous produce lignin.
• the native lignin content is 3 to 5% in leaves, 17 to 24% in herbaceous stems, 18 to 33% in woody stems (18 to 25% of hardwood of angiosperm trees, 27 to 33% soft wood of gymnosperm trees). It is less present in annual plants than in perennial plants, it is very present in trees.
• Native lignin is mainly located between cells, but a significant quantity is found within them. After cellulose (constituting 35 to 50% of terrestrial plant biomass) and hemicellulose (30 to 45%), lignin (15 to 25%) forms the third family of compounds in order of abundance in plants and in terrestrial ecosystems where dead or living plant biomass dominates.
• Lignin is a macromolecule whose possible structure is shown in Figure 1 [Fig. 1], Lignin, according to the invention, is extracted by cleavage of the 0-0-4 ether bonds of native lignin and therefore has a lower molar mass than that of the native lignin from which it comes, i.e. d. an average molar mass of less than 10,000 g. mol' 1 , preferably a molar mass of between 1,000 g. mol' 1 and 9,000 g. mol' 1 .
• the lignin can be chosen from alkaline lignins also called kraft lignins, lignosulfonates, organosolv lignins, sodium lignins, lignins coming from the bio-refining process of lignocellulosic raw materials, or a mixture of these.
• alkaline lignins also called kraft lignins, lignosulfonates, organosolv lignins, sodium lignins, lignins coming from the bio-refining process of lignocellulosic raw materials, or a mixture of these.
• the four groups of lignins available on the market are alkaline or kraft lignins, lignosulfonates, organosolv lignins (extracted lignins and sodium lignins).
• the fifth group is the so-called bio-refinery lignin which is a little different because it is not described by its extraction process, but rather by the origin of the process, e.g. by bio-refining and therefore may be similar or different from any of the other groups mentioned.
• the lignin, according to the invention is preferably alkaline lignin, also called kraft lignin.
• Figure 1 shows a possible structure of lignin, according to the invention, comprising both hydroxyl groups -OH and carboxyl groups -COOH.
• the reactive functional group present in the greatest quantity in a typical lignin is the hydroxyl group, which is either an aromatic hydroxyl group or an aliphatic hydroxyl group i.e. a primary alcohol function or an alcohol function secondary.
• the hydroxyl and carboxyl groups of lignin can react with cross-linking agents such as isocyanates or epoxides, amines or aldehydes leading to a cross-linked structure of the lignin, following different cross-linking mechanisms.
• these crosslinking agents are of less interest due to their toxicity (isocyanates, amines, formaldehyde) and/or their cost (epoxides, amines, aldehydes other than formaldehyde).
• thermosetting product based on ester lignin, in order to bind mineral fibers and natural organic fibers and then obtain insulating products with good mechanical properties.
• at least one lignin is mixed with at least one “non-polymeric” organic polycarboxylic acid.
• non-polymeric organic polycarboxylic acid is meant in the present application an organic polycarboxylic acid which is not a macromolecule consisting of the assembly of monomers having a molar mass of between 90 g. mol -1 and 350 g. mol -1 , linked together by covalent bonds in a repetitive manner.
• the thermosetting binder composition is preferably free of polymeric organic polycarboxylic acid.
• the non-polymeric organic polycarboxylic acid according to the invention can be chosen from dicarboxylic acids, in particular oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid.
• the non-polymeric organic polycarboxylic acid is chosen from maleic acid
• the Applicant has carried out tests to determine the respective proportions of lignin and non-polymeric organic polycarboxylic acid necessary to form the thermosetting binder composition based on ester lignin, in order to achieve, after dilution of said binder composition, a binder organic giving the final insulating product the best mechanical properties. These tests have shown that in the process for preparing the thermosetting binder composition according to the invention, the lignin(s) can represent at least 50% of the total weight of the organic acid(s). ) non-polymeric polycarboxylic(s) ⁇ ) and lignin(s).
• the one or more lignin(s) represent(s) from 50% to 80% of the total weight of the non-polymeric organic polycarboxylic acid(s) and lignin(s). Consequently, the non-polymeric organic polycarboxylic acid(s) advantageously represent(s) from 20% to 50% by weight of the total weight of the organic acid(s). ) non-polymeric polycarboxylic(s) and lignin(s).
• the mixture according to the process of the invention also comprises at least one organic monocarboxylic acid or at least one organic sulfonic acid.
• the organic monocarboxylic or sulfonic acid(s) represents at most 50% of the weight of the mixture consisting of the lignin(s), the ) non-polymeric organic polycarboxylic acid(s) and organic monocarboxylic or sulfonic acid(s). More preferably, the organic monocarboxylic or sulfonic acid(s) represent(s) from 5% to 50% of the weight of the mixture consisting of the lignin(s), the non-polymeric organic polycarboxylic acid(s) and organic monocarboxylic or sulfonic acid(s).
• the role of the organic monocarboxylic or sulfonic acid in the reaction mixture according to the invention is to adjust the pH of the lignin so that it is between 6.5 and 10.5, preferably between 8 and 9, between 10 and 20% in aqueous solution.
• the organic monocarboxylic acid may be chosen from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, pentanoic acid, a or lignin(s). , organic isovalerianic acid(s), hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic, tetradecanoic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, trans-vaccenic acid, linoleic acid, linolelaidic acid,
• the organic sulfonic acid is chosen from the group consisting of methylsulfonic acid, ethylsulfonic acid, propylsulfonic acid, butylsulfonic acid, methanedisulfonic acid, ethanedisulfonic acid, propanedisulfonic acid. , butanedisulfonic acid, benzenesulfonic acid and paratoluenesulfonic acid.
• the sulfonic acid is paratoluenesulfonic acid.
• At least one lignin is first mixed with at least one organic monocarboxylic or sulfonic acid in the presence of a water content which may be less than 5% by weight, preferably less than 1% by weight. , so that the pH of the lignin in solution is between 6.5 and 10.5, preferably between 8 and 9. Adjusting the pH of the lignin makes it possible to maximize its reactivity with the organic polycarboxylic acid non-polymeric without significantly affecting its solubility in water. Then, at least one non-polymeric organic polycarboxylic acid can then be added to said pre-mixture, preferably in the absence of solvent.
• the reaction mixture of the polycondensation between at least one lignin, in the presence of at least one monocarboxylic or sulfonic acid, with at least one non-polymeric organic polycarboxylic acid may contain less than 5% water by weight, preferably less than 1% water by weight and more advantageously the mixture is anhydrous.
• water makes it possible to homogenize the reagents in the reaction mixture. This water necessary for homogenization evaporates under the effect of the step of heating the reaction mixture.
• the mixture of at least one lignin, at least one organic monocarboxylic or sulfonic acid, and at least one non-polymeric organic polycarboxylic acid contains less than 5% by weight of aqueous solvents and /or organic, preferably less than 1% by weight of aqueous and/or organic solvents. Even more preferably, said mixture is free of solvents.
• the mixture may be free of polyols, and more particularly of hydrogenated sugars.
• the mixture may also comprise a catalyst which has the particular function of reducing the temperature of the pre-polymerization (crosslinking) between the lignin and the non-polymeric organic polycarboxylic acid.
• the catalyst may be a phosphorus-containing compound, for example an alkali metal hypophosphite salt, an alkali metal phosphite, an alkali metal polyphosphate, an alkali metal hydrogen phosphate, a phosphoric acid or an alkylphosphonic acid.
• the catalyst is sodium hypophosphite, sodium phosphite and mixtures of these compounds.
• the quantity of catalyst introduced into the mixture can represent up to 5% of the weight of the lignin and the non-polymeric organic polycarboxylic acid, preferably up to 3%, and advantageously is at least equal to 2%.
• the mixture is free of catalyst because the step of heating the mixture of at least one lignin, at least one organic monocarboxylic or sulfonic acid, and at least one organic polycarboxylic acid not -polymeric in fact makes it possible to avoid the use of such a catalyst, which is often toxic and can promote depolymerization and therefore the aging of the final insulating product.
• the reaction mixture is heated to a temperature of between 90°C and 170°C, preferably between 110°C and 150°C, for a period of between 5 seconds and 5 minutes, preferably between 15 seconds and 1 minute, so as to form at least one lignin ester that is soluble or dispersible in water.
• Heating of the mixture can be carried out using a thermoregulated enclosure or in a reactor equipped with a mechanical stirrer.
• the measuring device used by the applicant is the Discovery DSC model from TA Instruments.
• thermosetting binder composition based on lignin ester soluble or dispersible in water is obtained according to the process as described.
• thermosetting binder composition capable of being obtained by the process as described above, said binder composition contains at least one ester lignin soluble or dispersible in water, at least one residual lignin , at least one free residual non-polymeric organic polycarboxylic acid, and at least one free residual organic monocarboxylic or sulfonic acid.
• thermosetting binder composition advantageously contains at least one lignin ester with a molar mass of between 1000 g. mol -1 and 20,000 g.mol'1, preferably between 1000 g. mol' 1 and 10000 gmol' 1 ; the ester lignin being obtained by pre-polymerization i.e. by esterification reaction between aliphatic hydroxyl groups of lignin and the carboxyl groups of the non-polymeric polycarboxylic acid(s) and between hydroxyl groups of lignin and carboxyl groups of lignin itself.
• the content of free residual non-polymeric organic polycarboxylic acid can represent at most 45% by weight, relative to the total dry weight of the thermosetting binder composition and the content of free residual organic monocarboxylic acid or the content of organic sulfonic acid.
• free residual represents at most 45% by weight, relative to the total dry weight of the thermosetting binder composition.
• free residual is meant the content of non-polymeric organic polycarboxylic acid which has not reacted with lignin during pre-polymerization, or the content of organic monocarboxylic or sulfonic acid which has not exchanged d H + ion with lignin.
• the thermosetting binder composition obtained by the process contains, as mentioned above; at least one residual lignin, which means a quantity of lignin that has not reacted.
• thermosetting binder composition in particular has a pH of between 2 and 6, preferably between 2.5 and 5, at 10% in aqueous solution.
• the water content of the thermosetting binder composition may be less than 3% by weight, preferably less than 0.5% by weight.
• thermosetting binder composition as prepared according to the process of the invention:
• reagents “at least one lignin, at least one organic monocarboxylic or sulfonic acid, and at least one non-polymeric organic polycarboxylic acid”, in a sizing composition applied directly to any types of fibers (in other words without a pre-polymerization step), makes it possible to shorten, for a given oven temperature, the duration necessary for satisfactory hardening of the binder on the fibers the step of heating the assembly of said fibers which allows energy savings for heating the oven or the heating press and acceleration of the production line of insulating products, while obtaining insulating products with good mechanical properties.
• the third subject of the present application is a process for manufacturing an insulation product comprising mineral fibers or natural organic fibers linked by an organic binder, using a thermosetting binder composition according to the invention.
• This process includes the following steps:
• thermosetting binder composition as described above with water to a dry matter content of between 1% and 20% by weight, preferably between 2 and 10% by weight
• the sizing composition has good sprayability and can be deposited in the form of a thin film on the surface of the fibers in order to bond them effectively or the sizing composition must impregnate the fiber but not too much (with a contact angle slightly less than 90°).
• the sprayability of the sizing composition is directly linked to the possibility of diluting the concentrated thermosetting binder composition with a large quantity of water.
• the diluted sizing composition must be a solution or dispersion, stable over time, which does not give rise to demixing phenomena.
• the ability to dilute is characterized by “diluability” which is defined as the volume of deionized water that it is possible, at a given temperature, to add to a unit volume of the binder composition. before the appearance of a permanent disorder. It is generally considered that a binder composition is suitable for use as a sizing when its dilutability is equal to or greater than 1000%, at 20°C.
• the aqueous sizing composition obtained after dilution of the thermosetting binder composition based on ester lignin during step (a) of the aforementioned process may have a dry matter content of between 1% and 20% by weight, preferably between 2% and 10% by weight.
• the step of preparing the sizing composition advantageously comprises the addition of one or more known additives commonly used in the technical field of mineral fibers or natural organic fibers.
• these additives are chosen for example from anti-dust additives, silicones and coupling agents.
• the aqueous sizing composition can be applied to mineral fibers or natural organic fibers, in a quantity of between 1% and 20% by weight, preferably between 2% and 15% by weight, said quantity being expressed in dry matter. compared to the weight of the mineral fibers or natural organic fibers, in order to give the insulating product the desired mechanical properties.
• step (b) of applying the sizing composition to the mineral fibers or natural organic fibers can be carried out by spraying, in particular by means of spray nozzles. spraying, or by roller coating or by impregnation.
• the mineral fibers are preferably mineral wools and even more preferably glass, rock or slag wools, or mixtures thereof.
• the mineral fibers when they are mineral wools, they may contain a composition corresponding to the following formulation, in percentage by weight: Si ⁇ 2: between 30 and 50%, preferably between 35 and 45%, Na2 ⁇ : between 0 and 10%, preferably between 0.4 and 7%, CaO: between 10 and 35%, preferably between 12 and 25%, MgO: between 1 and 15%, preferably between 5 and 13%, CaO+MgO: between 11 and 40% cumulatively, AI2O3: between 10 and 27%,
• K2O between 0 and 2%, preferably between 0 and 1%
• Iron oxide between 0.5 and 15%, preferably between 3 and 12%
• other oxide(s) between 0 and 5% cumulatively, preferably less than 3%, the remainder consisting of unavoidable impurities.
• the mineral fibers can be glass fibers, or rock fibers, in particular basalt (or wollastonite).
• the mineral fibers according to the invention are aluminosilicate glass fibers, in particular aluminosilicate glass fibers comprising aluminum oxide, Al2O3, in a mass fraction of between 14% and 28%.
• the mineral fibers may be glass fibers containing a composition corresponding to the following formulation, in percentage by weight: Si ⁇ 2: between 50 and 75%, preferably between 60 and 70%, Na2 ⁇ : between 10 and 25%, preferably between 10 and 20%, CaO: between 5 and 15%, preferably between 5 and 10%,
• MgO between 1 to 10%, preferably between 2 and 5%
• B2O3 between 0 and 10%, preferably between 2 and 8%,
• AI2O3 between 0 and 8%, preferably between 1 and 6%, K2O: between 0 and 5%, preferably between 0.5 and 2%, Na2O and K2O together preferably representing between 12 and 20%, Iron oxide : between 0 and 3%, preferably less than 2%, preferably even less than 1%, other oxide(s): between 0 and 5% cumulative weight, preferably less than 3% cumulatively, the remains consisting of unavoidable impurities.
• the diameter of the mineral fibers is advantageously between 0.1 and 25 ⁇ m.
• the diameter of the natural organic fibers is advantageously between 5 and 100 pm, preferably between 10 and 50 pm and the length of these fibers is in particular between 0.1 and 900 mm, and more particularly between 10 and 120 mm.
• Natural organic fibers are advantageously fibers which are not thermoplastic, and which are naturally present in the biomass and may have undergone mechanical and/or chemical treatments. These fibers come from plant sources and are advantageously chosen from cotton and lignocellulosic fibers.
• the term “lignocellulosic fibers” means fibers of plant origin based on lignocellulosic material, that is to say comprising cellulose, hemicellulose and lignin.
• Lignocellulosic fibers include wood fibers, and fibers from other plants, for example hemp fibers, linen, sisal, cotton, jute, coconut, raffia, abaca, or even straw. cereals or rice straw.
• lignocellulosic fibers does not include lignocellulosic materials having been subjected to thermomechanical or chemical treatments for the manufacture of paper pulp.
• the lignocellosic fibers used in the present invention have therefore simply undergone a mechanical comminution treatment intended to reduce and/or control the size of the fibers.
• the lignocellulosic fibers are preferably softwood wood fibers, in particular pine, obtained by mechanical defibration. Their diameter is advantageously between 10 and 70 pm, preferably between 30 and 50 pm and they have a length ranging from 0.1 to 100 mm, preferably from 0.5 to 50 mm, in particular from 1 to 20 mm.
• the application of the sizing composition (b) preferably precedes step (c) of forming an assembly of mineral fibers or natural organic fibers, during which the sizing fibers are brought together, before being heated by consecutively or extemporaneously to harden the sizing composition thus forming the organic binder which binds the fibers.
• step (c) of forming an assembly of mineral fibers or natural organic fibers which can also be called the step of shaping all of the fibers, can be carried out by molding and/or compression.
• the mold used for molding the products must be made of a material capable of withstanding the temperature of the heating stage. It must also have a structure allowing the hot air from the cooking oven to easily penetrate the molded product.
• the mold can for example be formed from a metal mesh in the shape of a box.
• the metal mesh box is preferably filled with a volume of bulk fibers greater than its capacity and is then closed by a metal mesh cover.
• the fibers are thus more or less compressed depending on the excess filling volume. This volume excess filling of the box with the fibers is for example between 10% and 150%, preferably between 15 and 100% and in particular between 20 and 80%.
• step (c) of forming an assembly of fibers can be done for example by compression using a roller located at the entrance to the drying oven. cooking on a conveyor.
• the fibers can be assembled:
• molded fiber-based products for example duct or pipe linings, - in woven or non-woven textiles, such as non-woven glass or organic fiber mats.
• the fibers are natural organic fibers impregnated with aqueous sizing composition and said process further comprises, between step (b) and step (c), a step of drying the fibers which aims to evaporate enough water to make the sized or unsized fibers substantially non-sticky.
• the drying step can be done before step (b). This drying step can be carried out by heating, for example in a thermostatically controlled ventilated oven or by conveying the fibers using dry hot air. It is important to ensure that drying does not bring the natural organic fibers to too high a temperature which results in the softening of the dried sizing composition, or even in the beginning of crosslinking of the components of the sizing composition. .
• a drying temperature close to the boiling point of water is generally sufficient.
• the drying of the fibers impregnated with aqueous sizing composition is thus preferably carried out by heating at a temperature of between 70°C and 160°C, for a period of between 1 second and 10 seconds.
• the natural organic fibers obtained at the end of the drying step are surrounded by a sheath of dried sizing composition.
• Step (d) of heating the assembly of mineral fibers or natural organic fibers according to the process of the invention is preferably carried out at a temperature of between 90°C and 170°C for a period of between 1 minute and 10 minutes, preferably in a temperature-controlled chamber or a steam press.
• a temperature-controlled chamber or a steam press In the context of a thermo-regulated enclosure, this can be a forced air oven in which hot gases of controlled temperature are introduced into one or more compartments, or a heating mold with fluid circulation or heating resistance.
• pre-heating at least one lignin with at least one non-polymeric polycarboxylic organic acid in the presence of at least one monocarboxylic or sulfonic organic acid, in a preferably anhydrous medium and/or without solvents , at a temperature between 90°C and 170°C, for a period between 5 seconds and 5 minutes makes it possible to shorten the cooking time of the binder during step (d) of the process of manufacture of an insulating product, which represents energy savings.
• the insulating products obtained from the two processes described above had good mechanical properties.
• the invention concerns an insulation product capable of being obtained by the process of manufacturing an insulation product comprising mineral fibers or natural organic fibers linked by an organic binder as described above.
• Said insulating product obtained therefore comprises mineral fibers or natural organic fibers, linked using a binder obtained by hardening or crosslinking of a sizing composition obtained by dilution of a thermosetting binder composition based on lignin ester soluble or dispersible in water; itself obtained from at least one lignin, at least one monocarboxylic or sulfonic acid, and at least one non-polymeric organic polycarboxylic acid.
• the insulating product obtained has good mechanical properties.
• the insulating product obtained from natural organic fibers may have a thickness of between 10 and 300 mm, preferably between 35 and 240 mm, measured according to standard EN 823:2013 and a density of between 30 and 250 kg/m 3 , preferably between 100 and 250 kg/m 3 .
• the insulating product obtained can be used to make panels for the exterior insulation of buildings.
• the insulating products obtained from mineral fibers are preferably mineral fiber panels, in particular wool or rock, which may have a thickness of between 10 and 300 mm, preferably between 30 and 210 mm, measured according to the standard. EN 823:2013 and a density of between 10 and 120 kg/m 3 , preferably between 15 and 90 kg/m 3 .
• thermosetting binder composition No. 1 Preparation of a thermosetting binder composition No. 1 according to the invention
• thermosetting binder No. 1 35% of acetic acid by weight is added to 45% by weight of kraft A lignin. Then after homogenization of this pre-mixture, 20% of succinic acid by weight relative to the total weight of the lignin and the succinic acid is added. The mixture contains 3% by weight of water. The mixture is stirred and placed in an oven thermostatically controlled at 150°C, for 30 seconds, so as to provide the composition of thermosetting binder No. 1 and containing pre-polymerized ester A lignin. Said binder composition is very concentrated since the mixture is anhydrous and comprises 20% by weight of free residual acetic acid and less than 10% by weight of free residual succinic acid, relative to the total dry weight of the thermosetting binder composition. .
• the pre-cooked mixture containing the pre-polymerized lignin ester A is ground and diluted with water until a dilute solution with a dry matter content of 10% by weight is obtained.
• a non-prepolymerized aqueous sizing composition No. 2 is prepared, i.e. having not undergone pre-cooking, by simple mixing: acetic acid / kraft A lignin / succinic acid in a ratio 35/45/20 and water is added until obtaining a diluted solution having the same solids content of 10% by weight as sizing composition No. 2.
• a sizing composition No. 3 is prepared by emulsifying emulsifiable poly(methylenediphenyl isocyanate) (pMDI) with water.
• the dry matter content of the composition is equal to 60% by weight.
• An aqueous sizing composition No. 3 is prepared by simply mixing a phenolic resin (formaldehyde + phenol) / urea in an 80/20 ratio and water is added until a diluted solution having a dry matter content equal to 60% by weight.
• Each sizing composition described above 1, 2, 3 and 4 is then used to impregnate wood fibers.
• the quantity of aqueous sizing compositions 1, 2, 3 and 4 deposited on the wood fibers is equal to 7% by weight expressed as dry matter relative to the weight of the wood fibers.
• the impregnated wood fibers are then deposited uniformly in a stainless steel mold comprising several open cavities measuring 60 mm x 10 mm x 10 mm.
• Stainless steel bars measuring 60 mm x 10 mm x 8 mm are placed on the wood fibers and for each of the samples the assembly is heated for a determined period in a thermostatically controlled press at a given temperature and under a pressure of 10 bars.
• the mold is then allowed to cool to room temperature before removing the sample of lignocellulosic fibers formed (60 mm x 10 mm x 2 mm).
• the wood fiber specimens thus obtained have a density of approximately 180 kg/m 3 .
• the conservation modulus in bending (three-point bending) is then determined for each specimen by dynamic thermomechanical analysis (DMTA) using a “TA Instruments RSA-G2 Analyzer” device.
• DMTA dynamic thermomechanical analysis
• the samples are first dried for several hours in a dynamic vacuum desiccator (20 mbar).
• the operating parameters of the measuring device are as follows: Temperature: 25°C Poisson’s ratio: 0.45
• Oscillation frequency 1.0 Hz
• Each conservation modulus value is the average calculated over two to four individual measurement values.
• sizing composition No. 1 comprising the pre-polymerized ester A lignin obtained according to the process of the invention (i.e. after dilution of binder composition No. 1 obtained by pre-heating lignin A with succinic acid in the presence of acetic acid in an essentially anhydrous medium, in other words in a medium containing less than 5% water by weight) allows, for a given oven temperature equal to 150°C, to accelerate the time necessary for the hardening of the sizing composition on the wood fibers to form the organic binder (because duration: 4 minutes), in other words to obtain an insulating product with a modulus of conservation equivalent (around 100 MPa); compared to the use of a binder composition comprising line A which has not undergone pre-polymerization such as sizing composition No. 2 (duration: 10 minutes).
• the storage modulus obtained for the test pieces of wood fibers prepared in accordance with the invention is slightly lower (of the order of 100 MPa) compared to the wood fibers prepared using the compositions of known, but harmful, overly reactive sizing materials, such as poly(methylene diphenyl isocyanate) or phenol-formaldehyde urea resins (whose storage modulus is approximately 155 MPa); the mechanical properties of the wood fibers obtained according to the invention are good.
• a storage modulus of approximately 100 MPa for insulating products having a density of 180 kg/m 3 is satisfactory.
• Two other sizing compositions are prepared, according to the prior art, No. 5 and 5 bis, by successively introducing into a container 48 parts by weight of maltitol (as hydrogenated sugar), 52 parts by weight of citric acid , and 5 parts by weight of sodium hypophosphite sodium hypophosphite (catalyst) with vigorous stirring until the constituents are completely dissolved.
• each sizing composition described above n°1, 2, 5 and 5bis is then used to impregnate glass fibers.
• All sizing compositions 1, 2, 5 and 5bis contain 90% by weight of water and 10% by weight of dry materials. All compositions are used to form glass fiber insulation products.
• the conservation modulus in bending (three-point bending) is then determined for each sample by dynamic thermomechanical analysis (DMTA) using a “TA Instruments RSA-G2 Analyzer” device.
• DMTA dynamic thermomechanical analysis
• the samples are first dried for several hours in a dynamic vacuum desiccator (20 mbar).
• the operating parameters of the measuring device are the same as those mentioned above.
• sizing composition No. 1 comprising the pre-polymerized ester A lignin obtained according to the process of the invention (i.e. after dilution of binder composition No. 1 obtained by pre-heating lignin A with succinic acid in the presence of acetic acid in an essentially anhydrous medium, in other words in a medium containing less than 5% water by weight) allows, for a given oven temperature equal to 150°C, to accelerate the time necessary for the hardening of the sizing composition on the glass fibers to form the organic binder (because duration: 4 minutes), in other words to obtain an insulating product with a modulus of conservation equivalent (1.65 GPa); compared to the use of a binder composition comprising line A which has not undergone prepolymerization such as sizing composition No. 2 (duration: 10 minutes).
• sizing composition No. 1 comprising pre-polymerized lignin ester A makes it possible to obtain glass fiber papers having good mechanical properties (storage modulus equal to 1.65 GPa) , and much better than those obtained for glass fiber papers prepared using the known sizing compositions 5 and 5 bis based on hydrogenated sugar (storage modulus equal to 0.26 and 1.18 GPa).
• sizing composition No. 1 comprising the pre-polymerized ester A lignin makes it possible to lower the temperature of the heating step of the assembly of the glass fibers and to accelerate the duration of the heating step of the assembly of the glass fibers to form the organic binder, compared to the use of a binder composition based on hydrogenated sugar ( compositions 5 and 5bis).

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