Classifications

• • 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
  • C08J5/18—Manufacture of films or sheets
• • 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
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/02—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by the reacting monomers or modifying agents during the preparation or modification of macromolecules
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
  • C08L3/02—Starch; Degradation products thereof, e.g. dextrin
• • 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
  • C08J2203/00—Foams characterized by the expanding agent
  • C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
• • 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
  • C08J2203/00—Foams characterized by the expanding agent
  • C08J2203/10—Water or water-releasing compounds
• • 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
  • C08J2205/00—Foams characterised by their properties
  • C08J2205/04—Foams characterised by their properties characterised by the foam pores
  • C08J2205/042—Nanopores, i.e. the average diameter being smaller than 0,1 micrometer
• • 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
  • C08J2205/00—Foams characterised by their properties
  • C08J2205/04—Foams characterised by their properties characterised by the foam pores
  • C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
• • 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
  • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
  • C08J2361/02—Condensation polymers of aldehydes or ketones only
• • 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
  • C08J2399/00—Characterised by the use of natural macromolecular compounds or of derivatives thereof not provided for in groups C08J2301/00 - C08J2307/00 or C08J2389/00 - C08J2397/00

Definitions

• the present invention relates to thermoset solid foams obtained by reaction and chemical foaming of an expandable composition containing sugars and an acid catalyst.
• the manufacture of insulating products based on mineral wool generally comprises a step of manufacturing the glass or rock fibers by a centrifugation process. On their path between the centrifuge device and the fiber collection belt, the still hot fibers are sprayed with an aqueous sizing composition, also known as a binder, which is then subjected to thermosetting reaction at temperatures of about 200 ° C. .
• an aqueous sizing composition also known as a binder
• Phenolic resins used for several decades as binders have been replaced more and more by products from renewable sources and emitting little or no formaldehyde, a compound considered to be harmful to human health .
• application WO 2007/014236 discloses sizing compositions, or binders, based on reducing sugars and amines or ammonium salts which, inter alia by Maillard reaction, harden and bind the glass fibers. on which they are applied.
• the application WO2012 / 028810 discloses sizing compositions based on non-reducing sugars and metal salts of mineral acids capable of hardening and binding the glass fibers to which they are applied.
• WO2012 / 168621 discloses, in a similar manner, binders for glass fibers containing at least one non-reducing sugar, at least one non-reducing sugar dehydration catalyst, at least one an amine and at least one activated ethylenic unsaturation, these reactants being capable of reacting after application of the glass fibers directly after formation of the latter.
• the present invention is based on the surprising discovery that certain sugar-based sizing compositions, when heated in fairly concentrated form above a certain temperature (about 150 ° C), instead of spraying them on hot glass fibers, are highly foaming. Gas evolution occurs at the same time as the curing reaction.
• the liquid starting composition introduced into an open container and exposed to sufficient heat, increases in volume, thickens and eventually hardens, giving rise, after a few minutes to a rigid foam of dark color.
• the Applicant has carried out numerous tests to determine under which experimental conditions of compositions based on sugars, reducing or non-reducing, formed thermoset foams. Without wishing to be bound by a particular theory, the Applicant believes that the reaction involved in the curing of the foaming compositions of the present application is based on an acid catalysed reaction of dehydration of sugar, resulting in the formation of hydroxymethylfurfural ( HMF) capable of polymerizing.
• HMF hydroxymethylfurfural
• the present invention therefore relates to the use of a composition containing
• an acid catalyst chosen from strong acids, phosphoric acid and acidic mineral salts,
• thermoset solid foam usable as a thermal insulation product, comprising the following successive stages:
• an acid catalyst chosen from strong acids, phosphoric acid and acidic mineral salts,
• thermoset solid foam block (c) heating the expandable and thermosetting composition to a temperature of at least 140 ° C to form a thermoset solid foam block.
• the sugar usable in the present invention may be a reducing sugar or a non-reducing sugar.
• Reducing sugars are carbohydrates of formula C n (H 2 O) p having at least one aldehyde or ketone group (reducing group).
• Reducing sugars for use in the present invention include monosaccharides (monosaccharides) and osides (disaccharides, oligosaccharides, and polysaccharides).
• Hexoses namely sugars comprising six carbon atoms, such as glucose, mannose, galactose and fructose, are preferably used.
• Lactose or maltose are examples of disaccharides which can be used as reducing sugars.
• starch hydrolysates obtained by enzymatic hydrolysis or acid hydrolysis of starch are sucrose and trehalose.
• the acid catalyzing the dehydration of sugar can be a strong acid, that is to say an acid that dissociates completely when dissolved in water.
• the strong acids that can be used include hydrohalic acids, namely hydrochloric acid, hydroiodic acid and hydrobromic acid, sulfuric acid (H 2 SO 4 ), nitric acid (HNO 3 ), chloric acid and the like. (HCI0 3 ), perchloric acid (HClO 4 ), manganic acid (H 2 MnO 4 ), permanganic acid (HMnO 4 ), trifluoroacetic acid, and superacids including fluoroantimonic acid (HF.
• the phosphoric acid is not a strong acid (pKa1 of about 2), it can act as an acid dehydration catalyst provided it is used at a concentration of at least 0.1 mol / L, preferably at least 0.2 mol / L.
• the acidic catalyst is selected from strong acids and phosphoric acid
• the acid / sugar molar ratio is preferably less than 1/6, preferably between 1/40 and 1/8, in particular between 1/35 and 1/9, ideally between 1/34 and 1/10.
• the sugar used contains oligomers or polymers of monomeric carbohydrate units (for example starch hydrolysates containing monomeric units of glucose), the number of moles of sugars is equal to the number of moles of monomeric units.
• the acid catalyst may be an acidic mineral salt.
• the term "acidic mineral salt” means a mineral salt which, when introduced into demineralized water, makes it possible to lower the pH to a value of less than 3.
• These acidic mineral salts do not include the inorganic salts of the alkali and alkaline earth metals, but include a large number of transition metal salts.
• acidic inorganic salts are sulphates, nitrates, chlorides and bromides of aluminum, gallium, copper, zinc, silver, nickel, iron and lead,
• the Applicant has obtained good results with aluminum sulphate, copper sulphate and copper nitrate which are particularly preferred.
• the acidic mineral salts will preferably be used in a concentration such that the pH of the composition is less than or equal to 3, preferably less than 2.5 and ideally less than 2.
• the expandable and thermosetting compositions used in the present invention for the formation of solid foams generally contain water. This water essentially acts as a solvent for sugar.
• the expandable composition used in the process of the present invention does not need to be finely dispersed in air, it is less critical than in the case of a mineral fiber binder, to ensure that its viscosity is sufficiently low. While an aqueous binder for mineral fibers has, at the time of spraying, at least 90% or even 95% water, the expandable compositions of the present invention are much more concentrated and viscous.
• They advantageously contain at most 60% by weight of water, in particular at most 35% by weight, preferably at most 25% by weight, more preferably at most 15% by weight and ideally at most 5% by weight of water .
• the solids content of the foamable composition before heating is therefore at least 40% by weight, in particular at least equal to 65% by weight, preferably at least 75%, more preferably at least 85% by weight and ideally at least 95% by weight.
• the sugar represents in total at least 70%, preferably at least 80%, in particular at least 90% of the dry weight of the expandable composition.
• sugar and the acid catalyst are the major and essential components of the expandable composition, it may contain a number of other adjuvants and additives to improve the properties of the final thermoset foams or to reduce the cost of production.
• the total amount of these adjuvants and additives preferably does not exceed 30% of the dry weight of the expandable composition.
• the expandable composition may contain, for example, one or more surfactants to reduce the average size and dispersion of the pore sizes of the final foam or to facilitate incorporation of a filler.
• the expandable composition preferably contains from 1 to 15% by weight, preferably from 2 to 10% by weight, based on the dry weight of the total foamable composition, of one or more surfactants.
• the expandable composition used in the present invention may further contain up to 20% by weight, preferably up to 10% by weight, based on the dry weight of the total foamable composition, of one or more inorganic or organic fillers.
• the expandable composition may contain one or more other additives conventionally used in the industry for the processing and processing of polymers such as dyes, pigments, antibacterial or antifungal agents, flame retardants, UV absorbers, hydrophobic agents. These additives represent in total preferably at most 10% of the dry weight of the composition.
• reactive compositions known as such in highly diluted form, are therefore used in a manner totally different from that described in the documents of the state. of the technique mentioned in the introduction. They are not sprayed in the form of fine droplets on hot mineral fibers for the formation of a mat of fibers bonded together, but remain in compact form, not dispersed. Their solids content is considerably higher than that of the compositions of the state of the art.
• the thickness of the film, before heating, that is to say before expansion and curing is preferably at least 2 mm, in particular at least 5 mm, and more preferably at least 10 mm.
• the volume of the foam block formed can vary between very wide limits. When the expandable composition is used in a continuous process forming, for example, strips or profiles of insulating materials, it is potentially infinite. When the expandable composition is used to form discrete blocks, for example sheets or sheets of foams, the amount thereof is preferably such that the volume of each solid thermoset foam block is at least 500 cm 3 , preferably at least equal to 0.001 m 3 , in particular at least 0.01 m 3 .
• the foam block is preferably in the form of a plate.
• the reaction temperature will preferably be between 150 ° C and 180 ° C. This temperature is, of course, that measured at the heart of the reaction mixture.
• any conventional means known in the field of processing and processing of polymers such as hot air, thermal radiation, microparticles, can be used in principle. -ondes or the contact with a hot support (mold).
• the temperature of the heating means may be greater than the reaction temperature mentioned above, for example between 160 and 210 ° C.
• Another subject of the present invention is a solid foam that can be obtained by the method that is the subject of the present invention.
• the solid foams prepared by the process of the invention are of a dark brown to black color. Their density is between 30 and 60 kg / m 3 .
• They have a closed porosity with an average pore diameter, determined by X-ray tomography, between 100 and 800 nm.
• thermosetting expansible compositions are prepared by adding an aqueous solution of the acidic catalyst (acidic mineral salt) to a glucose monohydrate powder. The mixture is stirred at room temperature in order to disperse the powder.
• the acidic catalyst acidic mineral salt
• Table 1a shows the respective amounts of sugar and acidic mineral salt, expressed as solids, the mol / L concentration of the acid catalyst as well as the total solids content of the compositions prepared.
• compositions are introduced into a flat-bottomed aluminum dish (5 cm in diameter) in a film having a thickness of about 1 mm.
• the cups are introduced into an oven heated to 200 ° C. After 20 minutes, they are removed, allowed to cool to room temperature and the thickness of the formed foam observed: Scale of notation:
• the foams formed are all brown to black.
• compositions were prepared either omitting the acid catalyst or by replacing the mineral acids (AI 2 (S0 4) 3 and CuS0 4 Cu (N0 3) 2) inorganic salts do not allow to acidify the composition to a pH below 3.
• thermosetting expansible compositions are prepared by adding to 9 g of a glucose monohydrate powder 6 ml an aqueous solution of the acid catalyst (strong acid or phosphoric acid) having the concentration indicated in Tables 2a and 2b. The mixture is stirred at room temperature to disperse the powder.
• the acid catalyst strong acid or phosphoric acid
• Table 2a shows the mol / L concentration of the acid catalyst used as well as the total solids content of the compositions prepared.
• Each of the compositions is introduced into a flat-bottomed aluminum dish (5 cm in diameter) in a film having a thickness of about 1 mm.
• the cups are introduced into an oven heated to 200 ° C. After 20 minutes, they are removed, allowed to cool to room temperature and the thickness of the formed foam is observed.
• the rating scale is identical to that of Example 1.
• Hydrochloric acid, sulfuric acid and phosphoric acid used at a concentration greater than or equal to 0.1 mol / L give voluminous foams of brown to black color.
• nitric acid even at a high concentration, foams relatively less than other acids.
• the same acids are used in a concentration of 0.01 mol / l.
• Table 2b Strong acids and phosphoric acid (comparative)
• the Applicant has also carried out a series of tests by contacting D-glucose with increasing amounts of acetic acid (weak acid) and heating the mixture under the same conditions. Even at a concentration of acetic acid greater than 15 mol / L no formation of foam is observed.
• acetic acid weak acid

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Materials Engineering (AREA)
• Manufacturing & Machinery (AREA)
• Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Catalysts (AREA)

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• 2015
  • 2015-04-27 FR FR1553771A patent/FR3035402B1/fr active Active
• 2016
  • 2016-04-19 CA CA2981162A patent/CA2981162A1/fr not_active Abandoned
  • 2016-04-19 DK DK16723422.8T patent/DK3289008T3/da active
  • 2016-04-19 EP EP16723422.8A patent/EP3289008B1/fr active Active
  • 2016-04-19 JP JP2017555620A patent/JP6757331B2/ja active Active
  • 2016-04-19 US US15/569,095 patent/US20180201747A1/en not_active Abandoned
  • 2016-04-19 WO PCT/FR2016/050906 patent/WO2016174328A1/fr not_active Ceased
  • 2016-04-19 RU RU2017134540A patent/RU2716185C2/ru active
  • 2016-04-19 KR KR1020177030603A patent/KR20170141206A/ko not_active Ceased

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