Classifications

• • 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
  • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
  • C09J161/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C09J161/04, C09J161/18 and C09J161/20
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
• • 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
  • C03C13/00—Fibre or filament compositions
  • C03C13/06—Mineral fibres, e.g. slag wool, mineral wool, rock wool
• • 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
  • C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
  • C03C25/34—Condensation polymers of aldehydes, e.g. with phenols, ureas, melamines, amides or amines
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
  • C08K5/136—Phenols containing halogens
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/21—Urea; Derivatives thereof, e.g. biuret
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
  • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
• • D—TEXTILES; PAPER
  • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
  • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
  • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
  • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
  • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
  • D04H1/4209—Inorganic fibres
• • D—TEXTILES; PAPER
  • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
  • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
  • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
  • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
  • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
  • D04H1/4209—Inorganic fibres
  • D04H1/4218—Glass fibres
• • D—TEXTILES; PAPER
  • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
  • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
  • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
  • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
  • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
  • D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
• • 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
  • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
  • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
  • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
  • C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
• • 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
  • C08G2330/00—Thermal insulation material
• • 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
  • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
  • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
  • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
  • C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol

Definitions

• the present invention relates to an amino resol resin, stabilized by a solubilizing agent chosen from water-soluble aromatic polyols, an aqueous binder composition prepared from this resin, a process for manufacturing an insulation product based on fibers, in in particular based on mineral wool, using this aqueous binder composition, as well as a thermal and / or acoustic insulating product obtained by this manufacturing process.
• a solubilizing agent chosen from water-soluble aromatic polyols
• aqueous binder composition prepared from this resin
• a process for manufacturing an insulation product based on fibers, in in particular based on mineral wool using this aqueous binder composition, as well as a thermal and / or acoustic insulating product obtained by this manufacturing process.
• a water-soluble polyhydroxy aromatic compound as a resin solubilizer, or cosolvent, allows partial or complete replacement of the urea commonly used in this type of resin.
• the manufacture of mineral wool-based insulation products generally includes a step of manufacturing glass or rock fibers by a centrifugation (fiberizing) process. On their path between the centrifuge device and the fiber collection belt, the still hot fibers are sprayed with an aqueous binder composition, also called a sizing composition, which then undergoes a thermosetting reaction at temperatures of about 200 ° C.
• aqueous binder composition also called a sizing composition
• Aqueous binder compositions are prepared shortly before use by diluting a concentrated thermosetting resin with water and adding various commonly used additives (coupling agents, anti-dust additives, hydrophobic agents, catalysts).
• Concentrated thermosetting resins must be stable on storage, i.e. they must not precipitate and must retain their ability to be diluted with water for as long as possible when preparing the sizing composition. . It is generally considered that a concentrated thermosetting resin is stable when, after a storage period of at least 14 days at a temperature between 12 and 18 ° C, it is still in the state of solution free from precipitate and retains a solid state. dilutability of at least 1000% (the addition of 9 volumes of water to 1 volume of resin gives a clear solution, free of permanent haze).
• thermosetting resins are phenolic resins belonging to the family of resols. In the technical field of phenol-formaldehyde resins, there are mainly two families, namely:
• the phenolic resins of the present invention belong to this second family.
• Resol resins are obtained in a basic medium by reacting phenol with an excess of formaldehyde, the formaldehyde / phenol molar ratio typically being between 2 and 4, each molecule of phenol potentially being able to react with three molecules of formaldehyde.
• the resol resins thus obtained contain numerous methylol functions carried by an aromatic nucleus, which constitute the sites of crosslinking by dehydration / release of formalin. These resins consist essentially of phenol / formaldehyde (PF) condensate, residual phenol and residual formaldehyde. In an acidic medium they react, that is to say polymerize, very quickly at room temperature and precipitate. To reduce the amount of residual formaldehyde and improve the stability of the resins on storage, it has been proposed first to add to the resin, after neutralization of the catalyst, a sufficient amount of urea which reacts with the residual free formaldehyde to form urea-formaldehyde (UF) condensates.
• UF urea-formaldehyde
• Such a resin therefore contains phenol-formaldehyde (PF) and urea-formaldehyde (UF) condensates.
• PF phenol-formaldehyde
• UF urea-formaldehyde
• amino resols or “amino phenolic resins”, stable on storage and essentially free from urea-formaldehyde (UF) condensates.
• These amino phenolic resins are water-soluble resins which are stable at acidic pH, even at a very acidic pH of between 1 and 2. This good stability is obtained thanks to an additional reaction step which consists in reacting the resols consisting essentially of phenol / formaldehyde condensates, phenol and formaldehyde with an amine, preferably a monoalkanolamine, and in particular monoethanolamine.
• This alkanolamine reacts according to the Mannich reaction with phenol / formaldehyde (PF) condensates and with residual phenol and formaldehyde to form phenol / formaldehyde / amine (PFA) condensates.
• PF formaldehyde
• PFA formaldehyde / amine
• the reaction mixture can be acidified without causing polymerization at room temperature.
• These amino resols are therefore considered to be stable in an acidic medium.
• Their synthesis is described in applications WO2008 / 043960 and WO2008 / 043961 by the Applicant. They are also distinguished by the fact that they are free from urea-formaldehyde condensates. As explained previously, these undesirable UF condensates are present in large amounts in many phenolic resins of the state of the art and exhibit insufficient thermal stability, releasing formaldehyde by thermal decomposition.
• up to 25% by weight preferably between 10% and 20% by weight of urea
• Urea is then used mainly as a cosolvent or solubilizing agent and further reduces the cost of sizing compositions and products obtained. Urea also traps traces of formaldehyde which may still be present at the end of the synthesis (less than 0.2%).
• Amino phenolic resins in aqueous solution stabilized with urea (solubilizing agent), have thus been used for more than ten years by the Applicant for the manufacture of insulation products based on mineral fibers which release very low amounts of formaldehyde during production and during use.
• the aim of the present invention has been to provide a solubilizing agent, or cosolvent, different from urea, which
• - is capable of stabilizing an aqueous solution of amino phenol-formaldehyde resin at least as effectively as urea (absence of crystals and dilutability greater than 1000% for at least 14 days),
• CMR toxic to reproduction
• the Applicant has tested a large number of organic compounds, in particular amino acids, (poly) aldehydes, aromatic and non-aromatic polyols and carbohydrates, but only water-soluble aromatic polyols have proved to be sufficiently effective to stabilize amino phenolic resins. concentrated solution in water for at least 14 days.
• the present invention therefore relates to a stabilized resol resin comprising
• a water-soluble amino phenolic resin preferably consisting essentially of phenol-formaldehyde (PF) condensate and phenol-formaldehyde-amine (PFA) condensate, and
• aqueous binder composition prepared from the resol resin stabilized by dilution and addition of current additives.
• This aqueous binder composition therefore comprises water (of dilution), the stabilized resol resin defined above, and one or more additives chosen from coupling agents, anti-dust oils or emulsions, hydrophobic agents and hardening reaction accelerators.
• a subject of the invention is a process for manufacturing an insulating product based on organic or mineral fibers using the aqueous binder composition, as well as an insulating product obtained by this process, in which the organic or mineral fibers are bonded. between them by an insoluble and infusible binder obtained by curing the ingredients of the aqueous binder composition.
• the stabilized resol resin which contains the amino phenolic resin, water, and the solubilizing agent, and the binder composition prepared by diluting the stabilized resol resin and adding known additives such as coupling agents, anti -dust, hydrophobic agents and catalysts or accelerators.
• the stabilized resol resin is therefore the concentrated resin, resulting from the synthesis, which will be stored, transported, marketed and used as a thermosetting component for the preparation of the aqueous binder composition, shortly before the implementation of the process of manufacturing.
• Its water content is generally between 30 and 60%, preferably between 35 and 55% by weight and in particular between 40 and 50% by weight.
• a water soluble aromatic polyol used to describe the solubilizer includes both pure compounds, used alone, and mixtures of two or more water soluble aromatic polyols.
• the resin also contains small amounts of salt resulting from the neutralization of the catalyst (strong base such as NaOH or KOH) by an acid, for example sulfamic acid, at the end of the synthesis of the resin.
• strong base such as NaOH or KOH
• an acid for example sulfamic acid
• the adjective "stabilized" relating to the resole resin means in the present invention that the resin remains for at least 14 days of storage at a temperature of 12 to 18 ° C in the form of a clear solution, free of precipitate, and that it retains during this period a dilutability in water of at least 1000%.
• the solubilizing agent used in the present invention to at least partially replace urea, used hitherto, is chosen from water-soluble aromatic polyols which are preferably not part of the chemical compounds carcinogenic, mutagenic or toxic for reproduction (CMR ).
• CMR toxic for reproduction
• aromatic polyols water-soluble are those having a solubility in water at 20 ° C greater than 20 g / L, preferably greater than 50 g / L.
• Aromatic character is an important aspect of the solubilizing agents used in the present invention.
• the Applicant has in fact tested a certain number of non-aromatic polyhydroxy compounds such as glycerol, carbohydrates and hydrogenated sugars (alditols) which are well soluble in water and not classified as CMR, but are ineffective in stabilizing the resin.
• phenolic that is to say to preserve the dilutability of the resin for at least 14 days of storage at a temperature of 12 - 18 ° C and to prevent its crystallization when stored at low temperature (3 ° C). It is probable that the aromatic character of polyols increases their affinity for the phenolic resin, itself aromatic, and thus increases the solubility of the latter in water.
• the solubilizing agents used in the present invention have at least two hydroxyl groups.
• the hydroxyl groups are preferably located directly on the aromatic ring.
• the solubilizing agent may have a monocyclic (benzene) or polycyclic (naphthalene, anthracene) aromatic ring. It is advantageously monocyclic or bicyclic, preferably monocyclic, and carries at least two, preferably two or three hydroxyl functions, located directly on the aromatic nucleus.
• polyhydroxylated aromatic compounds which can be used as solubilizing agent in the present invention, unsubstituted polyphenols such as resorcinol, phloroglucinol and pyrocathecol, substituted polyphenols bearing aldehyde, carboxylic acid or alkyl substituents. and ether, such as gallic acid, 3,4-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,4-dihydroxybenzaldehyde, 2-hydroxy-3-methoxybenzaldehyde, 4-methoxybenzene-1 , 2-diol, 4-methoxybenzene-1, 3-diol and mixtures thereof.
• unsubstituted polyphenols such as resorcinol, phloroglucinol and pyrocathecol
• substituted polyphenols bearing aldehyde carboxylic acid or alkyl substituents.
• ether such as gallic acid, 3,4-dihydroxybenzoic acid,
• resorcinol and phloroglucinol are particularly preferred. Indeed, these compounds are able both to dissolve the amino phenolic resin in water and to trap the traces of free formaldehyde (less than 0.2%) which could be present in the amino phenolic resin at the end of the process. synthesis.
• resorcinol and phloroglucinol are indeed capable of reacting with formaldehyde and of forming aromatic compounds with methylol function (s) capable of reacting with the PF and PFA condensates of the phenolic resin.
• the addition of urea to the resol resin is in principle superfluous and the stabilized resol resin of this present invention.
• the invention is then preferably urea-free.
• the total absence of urea guarantees the absence of ammonia emanations (NFb) during the thermal curing stage of the binder and during the use of the insulation product produced.
• solubilizing agent which, unlike resorcinol, is not able to trap traces of formaldehyde
• This addition can be done before or after the addition of the polyhydroxylated aromatic solubilizing agent, but must be done after the end of the synthesis of the amino phenolic resin consisting essentially of PF and PFA condensates, that is to say after cooling and neutralization of the reaction solution. In fact, the formation of urea-formaldehyde condensate should be avoided during resin synthesis.
• the resin preferably contains less than 15% by weight, for example 0.1 to 15% by weight, preferably less than 15% by weight. 10% by weight, for example 0.5 to 10% by weight, in particular less than 5% by weight, for example 1 to 5% by weight of urea, based on the total dry weight of the stabilized resole resin (resin amino phenolic + aromatic polyol + urea).
• the urea / aromatic polyol weight ratio is then generally between 1/4 and 3/1, preferably between 1/3 and 2/1, in particular between 1/2 and 1.
• the phenolic resin used in the present invention contains basic (protonable) amine functions and is stable in an acidic medium.
• phenolic resins with amine functions are known and their preparation is described in detail in applications WO2008 / 043960 and WO2008 / 043961 by the Applicant. They are essentially made up of of phenol / formaldehyde (PF) and phenol / formaldehyde / amine (PFA) condensates and are distinguished in particular by the absence of urea-formaldehyde (UF) condensates. As explained in the introduction, these urea-formaldehyde condensates are present in large amounts in many other phenolic resins of the state of the art and have insufficient thermal stability, releasing formaldehyde and ammonia by thermal decomposition.
• PF phenol / formaldehyde
• PFA phenol / formaldehyde / amine
• the stabilized resol resin of the present invention advantageously has a pH of between 1.0 and 6.5, preferably between 1.5 and
• aqueous binder compositions prepared by diluting the stabilized resol resin with water generally exhibit a less acidic pH than the resol resins, typically between 3 and 7, in particular between 3.5 and
• the dilution water used for the preparation of the binder compositions from the stabilized resol resin may come in part from the wash water recycled from the insulation product manufacturing facilities.
• the binder composition of the present application therefore contains water, a stabilized resol resin and one or more additives, commonly used in the field of insulation products based on mineral wool.
• additives are chosen among others from coupling agents, in particular functional silanes such as aminosilanes or epoxysilanes, anti-dust oils or oil emulsions, in particular mineral oils, hydrophobic agents such as polyorganosiloxanes (silicones) reactive or not, and the accelerators of the curing reaction.
• coupling agents in particular functional silanes such as aminosilanes or epoxysilanes, anti-dust oils or oil emulsions, in particular mineral oils, hydrophobic agents such as polyorganosiloxanes (silicones) reactive or not, and the accelerators of the curing reaction.
• the binder composition preferably has a dry matter content of between 2 and 25% by weight, preferably between 3 and 15% by weight. It therefore contains 75 to 98% by weight, in particular 85 to 97% by weight of water.
• the aqueous binder composition is urea free.
• the binder composition is applied in an amount such that the content of insoluble and infusible binder in the final product obtained after curing thermal, or between 2% and 20% by weight, preferably between 3% and 15% by weight, in particular between 4 and 12% by weight.
• a subject of the present invention is also a process for manufacturing an insulating product based on mineral or organic fibers. This process comprises the following successive steps
• an aqueous binder composition according to the invention on mineral or organic fibers, preferably mineral fibers, and
• the mineral fibers are advantageously chosen from fibers of mineral wool, in particular of glass or rock wool.
• the binder composition is sprayed onto the mineral fibers at the outlet of the centrifugation device (fiberizing) and before the mineral fibers are collected on the receiving organ ( forming) in the form of a web of fibers which is then treated in an oven at a temperature allowing the crosslinking of reactive ingredients and the formation of an infusible binder (baking).
• This crosslinking / thermal curing step is carried out by heating to a temperature greater than or equal to 180 ° C, preferably between 190 ° C and 220 ° C, for a period of between 20 seconds and 300 seconds, preferably between 30 and 250 seconds.
• the firing temperature is generally lower than that used for cooking products based on mineral fibers in order to preserve the organic fibers from possible thermal degradation.
• the cooking temperatures are, for example, between 150 and 200 ° C.
• the cooking time is usually between several minutes and several tens of minutes, for example between 5 and 50 minutes, preferably between 10 and 30 minutes.
• the baking of the inorganic or organic fibers can be done immediately after application of the binder composition to the fibers and collection of the sized fibers on a conveyor belt, for example by passing through a thermostatically controlled oven at the temperature of desired cooking.
• the process of the present application also covers an embodiment where the mat of sized fibers is not cured immediately but is packaged, for example partially dried, cut, compressed, shaped and packaged, with a view to a step of separate baking of the manufacturing step of the bonded fiber mat.
• the packaging material must be chosen so as to allow the storage and / or transport of these intermediate products (fibers sized with an unhardened binder) for an additional process step, implemented subsequently or in a different location, and comprising the thermal hardening of the binder, optionally after forming of the intermediate product, for example in a mold.
• the packaging material is preferably a plastic film.
• the temperature is gradually reduced over a period of 30 minutes to 60 ° C. while simultaneously adding to the reaction mixture, in a regular manner, 71.5 g of monoethanolamine (1.17 moles).
• the temperature is maintained at 60 ° C for 15 minutes, the mixture is cooled to 35 ° C about 30 minutes and solid sulfamic acid is added over 60 minutes until the pH is 5.0. Sulfamic acid in 15% solution is then used to lower the pH to 4.5. If necessary, the solids content of the liquid resin by weight is adjusted to 58% with water.
• the resin obtained has the appearance of a clear aqueous composition: it has a free formaldehyde level equal to 0.1%, a free phenol level equal to 0.5% (these levels being expressed relative to the total weight of liquid) and a dilutability greater than 2000%. It is called unstabilized resol resin.
• the unstabilized resol resin is divided into several batches and a stabilizing agent to be tested is added to each batch in an amount equal to 20 parts per 80 parts of dry weight of resin, for those of sufficient solubility, and in an equal amount. at 10 parts by weight per 80 parts by dry weight of unstabilized resole resin for those with insufficient solubility (see Table 1). Stirred at room temperature until complete dissolution to obtain so-called “stabilized” resol resins, the stability of which is to be evaluated.
• Two batches of stabilized resol resin are also prepared by adding, under the same conditions, respectively 5 parts of resorcinol and 5 parts of phloroglucinol to 80 parts of unstabilized resol resin.
• the level of free formaldehyde in resol resins is also evaluated in order to verify the ability of the stabilizing agent to react with residual formalin (function of formaldehyde scavenging agent).
• resole resin For this, approximately 1 g of resole resin is taken in a 100 mL volumetric flask, and the mass m taken is precisely noted. Make up with distilled water to the mark. The level of formalin is determined using a LANGE DR6000 colorimeter fitted with an LCK 325 formalin quantification kit, following the supplier's recommendations.
• the measurement is carried out on 1 mL of the sample taken from the preparation flask.
• the result A obtained by the colorimeter is given in mg / L.
• the rate of free formaldehyde is calculated as follows:
• the level of free formaldehyde is given as a% of the sample, expressed at ⁇ 0.01%. Any result less than 0.01% is noted ⁇ 0.01%.
• the inlet of a plunger is plugged into the flat-bottomed flask so as to sweep the surface of the sample at an air flow rate of 1 L / min.
• the whole is placed in a ventilated oven preheated to 215 ° C.
• the outlet of the plunger is connected to three bubblers arranged in series outside the oven each containing 100 mL of a 0.02 N sulfuric acid solution. After cooking for one hour, the contents of the bubblers are analyzed by ion chromatography to quantify the amount of ammonia trapped.
• resorcinol and phloroglucinol have a stabilizing power of the resol resin at least equal to or even greater than that of urea: dilutability greater than 1000% and stabilization on crystallization over an equivalent period. or longer are indeed observed.
• Resorcinol and phloroglucinol are also capable, like urea, of reacting with the free formaldehyde contained in the unstabilized resole resin.
• ammonia emissions are greatly reduced (from 310 mg / m 3 to less than 20 mg / m 3 ).

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• Geochemistry & Mineralogy (AREA)
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• Dispersion Chemistry (AREA)
• Phenolic Resins Or Amino Resins (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

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• 2020
  • 2020-06-29 FR FR2006774A patent/FR3111900B1/fr active Active
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  • 2021-06-29 JP JP2022581616A patent/JP2023532739A/ja active Pending
  • 2021-06-29 US US18/013,575 patent/US20230340180A1/en active Pending
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  • 2022-12-26 CO CONC2022/0018901A patent/CO2022018901A2/es unknown

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