EP2603550A1 - Matériaux stables à hautes températures et à l'humidité présentant des propriétés d'isolation améliorées à base de mousses et de silicates dispersés - Google Patents

Matériaux stables à hautes températures et à l'humidité présentant des propriétés d'isolation améliorées à base de mousses et de silicates dispersés

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Publication number
EP2603550A1
EP2603550A1 EP11740682.7A EP11740682A EP2603550A1 EP 2603550 A1 EP2603550 A1 EP 2603550A1 EP 11740682 A EP11740682 A EP 11740682A EP 2603550 A1 EP2603550 A1 EP 2603550A1
Authority
EP
European Patent Office
Prior art keywords
foam particles
foam
weight
particles
hollow microspheres
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP11740682.7A
Other languages
German (de)
English (en)
Inventor
Tatiana Ulanova
Sabine Fuchs
Bernhard Schmied
Klaus Hahn
Murray Orpin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP11740682.7A priority Critical patent/EP2603550A1/fr
Publication of EP2603550A1 publication Critical patent/EP2603550A1/fr
Withdrawn legal-status Critical Current

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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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/224—Surface treatment
    • 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
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • 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
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • C08J9/42—Impregnation with macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/02—Polysilicates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • 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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/038—Use of an inorganic compound to impregnate, bind or coat a foam, e.g. waterglass
    • 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
    • C08J2203/22—Expandable microspheres, e.g. Expancel®
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • 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
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/06—Polystyrene

Definitions

  • the invention relates to coated foam particles, to processes for the production of foam moldings and to their use.
  • Particulate foams are usually obtained by sintering foam particles, for example prefoamed expandable polystyrene particles (EPS) or expanded polypropylene particles (EPP) in closed forms by means of steam.
  • EPS prefoamed expandable polystyrene particles
  • EPP expanded polypropylene particles
  • Flame-retardant polystyrene foams are generally equipped with halogen-containing flame retardants, such as hexabromocyclododecane (HBCD).
  • halogen-containing flame retardants such as hexabromocyclododecane (HBCD).
  • HBCD hexabromocyclododecane
  • the approval as an insulating material in the construction sector is limited to certain applications.
  • One of the reasons for this is the melting and dripping of the polymer matrix in case of fire.
  • the halogen-containing flame retardants can not be used without restriction in terms of their toxicological properties.
  • WO 00/050500 A1 describes flameproofed foams of prefoamed polystyrene particles which are mixed together with an aqueous sodium silicate solution and a latex of a high molecular weight vinyl acetate copolymer, poured into a mold and dried in air while shaking. This results in only a loose bed of polystyrene particles that are glued together at a few points and therefore have only insufficient mechanical strength.
  • WO 2005/105404 A1 describes an energy-saving process for the production of foam moldings, in which the prefoamed foam particles are coated with a resin solution which has a lower softening temperature than the expandable polymer. The coated foam particles are then sealed in a mold using external pressure or by post-expansion of the foam particles with hot steam.
  • WO 2007/023089 A1 describes a process for producing foam moldings from prefoamed foam particles which have a polymer coating.
  • the preferred polymer coating used is a mixture of a waterglass solution, waterglass powder and a polymer dispersion.
  • the polymer coating may optionally include hydraulic binders based on cement or metal salt hydrates, for example aluminum hydroxide may be added.
  • a similar process is described in WO 2008/0437 A1, according to which the coated foam particles can be dried and then processed into a fire and heat-resistant foam moldings.
  • WO 00/52104 A1 relates to a fire protection coating which forms an insulating layer in the event of fire and based on foam-forming and carbon-forming substances in the event of fire, which contains melamine polyphosphate as the blowing agent. Information on water resistance is not included.
  • WO 2008/043700 A1 relates to a process for producing coated foam particles with a water-insoluble polymer film.
  • WO 2009/037116 relates to a coating composition for foam particles containing a clay mineral, an alkali metal silicate and a film-forming polymer.
  • Hydraulic binders such as cement bind in aqueous slurry with carbon dioxide even at room temperature. As a result, embrittlement of the foam plate occur.
  • the foam panels produced according to the cited prior art do not withstand temperatures of over 800 ° C in case of fire and collapse in case of fire.
  • the known coating compositions are in need of improvement in view of the simultaneous improvement of flame / heat resistance and their water resistance in water exposure or in increased humidity.
  • Many known materials lose their original shape after a short time in the case of direct water exposure.
  • a standard fire test is performed, such materials often completely lose their structural integrity. As a rule, this leaves powdery mixtures which no longer meet the technical requirements.
  • WO 2004/022505 describes the preparation of an agglomerate-free, ceramic nanoparticle dispersion which enables homogeneous and uniform distribution of the nanoparticles in material systems to be prepared or supplemented.
  • EP 1043094 A1 describes a Si0 2 dispersion as a binder. It is about processes for the production of castings and investment materials.
  • DE 19534764 A1 describes thin, crack-free, preferably transparent and colorless SiO 2 films, a process for their preparation according to the sol-gel process and their use, for.
  • US-A-3783020 describes an anti-hygroscopic coating of electrodes with colloidal Si0 2 .
  • US-A-4045593, EP-A-1537940, EP-A-468778 describe colloidal silica containing binders for various fluxes.
  • the invention therefore an object of the invention to provide a high-temperature-stable material based on foams available, in addition to good water resistance with prolonged exposure to moisture and good thermal insulation properties and improved mechanical properties, in particular a lower density, offers and thus easy to handle and good isolated.
  • the invention relates to foam particles, preferably of a polyolefin or styrene polymer, characterized in that the foam particles are coated with a combination of a silicate-containing coating, hollow microspheres and optionally nanoscale Si0 2 particles.
  • hollow microspheres are understood to be spheres whose surface consists of a polymer.
  • the interior of the ball is hollow and can be filled with a propellant gas.
  • the hollow microspheres used have a flexible outer layer, which means that the hollow microspheres can easily be compressed. They are so elastic that they are several Lasther. Resist pressure changes without bursting its shell.
  • the hollow microspheres are a mixture of expanded and unexpanded hollow microspheres, the expanded hollow microspheres being obtained by expansion of expandable hollow microspheres.
  • Such hollow microspheres consist essentially of a gas-tight, polymeric outer layer and a liquid or gaseous propellant enclosed therein.
  • the outer layer of the expandable or the expanded hollow microspheres usually behaves like a thermoplastic.
  • the homopolymers and / or copolymers used in the outer layer may be linear, branched or crosslinked. Polymers and copolymers containing acrylic acid, methacrylic acid, styrene, vinylidene chloride, acrylonitrile, methacrylonitrile and the like, as well as mixtures thereof, are often used for the outer layer.
  • the propellants used are preferably lower hydrocarbons such as propane, n-butane, isobutane, isopentane, n-pentane, neopentane, hexane, heptane and petroleum ether and halogenated hydrocarbons such as methyl chloride, methylene chloride, trichlorofluoromethane and dichlorodifluoromethane.
  • the expandable hollow microspheres can be prepared by known methods, as described for example in US 3,615,972. The average diameter of the expandable hollow microspheres usually increases by 4 to 6 times during expansion.
  • Suitable hollow microspheres in expanded, expandable and non-expandable form are also commercially available, for example under the trade name "EXPANCEL®” from Akzo Nobel.
  • the expandable hollow microspheres have an outer layer of an acrylate / methacrylate copolymer and contain 10 to 30 wt .-% blowing agent based on hollow microsphere polymer plus propellant, preferably isopentane.
  • the hollow spheres to be used according to the invention can be produced in particular in the following steps:
  • the polymerizable substance with the blowing agent is then preferably dispersed in an aqueous medium to form droplets no larger than the size of the desired hollow spheres.
  • the thus formed dispersion is stabilized, in particular, by adding a thickening agent, and the thus stabilized dispersion is subjected to polymerization to form hollow spheres.
  • Particularly preferred hollow spheres in the context of the present invention essentially have a spherical shape and a diameter of preferably from 1 to 600 ⁇ m, in particular from 2 to 60 ⁇ m.
  • the hollow microspheres can be prefoamed before use or used in a non-prefoamed state.
  • the hollow microspheres and the silicate-containing coating are preferably mixed together and applied to the foam particles.
  • the combination according to the invention of a silicate-containing coating and hollow microspheres preferably contains from 20 to 60, in particular from 25 to 40, parts by weight of hollow microspheres per 100 parts by weight of a silicate-containing coating.
  • the silicate-containing coating contains a ceramic material a), an alkali silicate b). Furthermore, the coating preferably contains a film-forming polymer c) and optionally nanoscale Si0 2 particles d).
  • the ceramic materials to be used according to the invention ceramize in case of fire, that is to say not yet during the production of the coating compositions according to the invention and foam particles.
  • Preferred ceramic materials are clay minerals and calcium silicates, in particular the mineral wollastonite.
  • the coating according to the invention consists at least substantially of the components indicated a) to m) with the parts by weight given there. In a particularly preferred embodiment, these parts by weight complement each other to 100%, wherein the weight percentages then present are based on the solids content of the coating.
  • the coating composition contains 1. 0 to 80 parts by weight of a ceramic material, in particular wollastonite 2. 60 to 80 parts by weight of an aluminum silicate, especially kaolin
  • colloidal silica having a surface area of 50 m 2 / g (Levasil ®) 50/50
  • the weight ratio of sodium silicate / potassium silicate is about 0.5: 1 to 1: 0.5, in particular 1: 1.
  • the coating composition is preferably used as an aqueous dispersion, wherein the water content including the water bound, for example, as water of crystallization is preferably in the range of 10 to 40, in particular 15 to 30 wt .-% based on the total aqueous dispersion.
  • e) contains a hydrophobizing amount of a silicon-containing compound, in particular a silicone, in particular 0.2 to 5 parts by weight.
  • a silicon-containing compound in particular a silicone, in particular 0.2 to 5 parts by weight.
  • this is a silicone emulsion with silicone particles of different sizes.
  • a preferred coating composition contains a) 30 to 50 parts by weight of a ceramic material
  • the amounts given above each refer to solids based on solids of the coating composition.
  • the components a) to e) or a) to f) preferably add up to 100% by weight.
  • the weight ratio of the ceramic material to alkali metal silicate is present in the coating composition ranges from 1: 2 to 2: 1.
  • a ceramic-forming clay minerals a) are particularly suitable allophane Al 2 [Si0 5] 0 3 ⁇ n H 2 0, kaolinite AI 4 [(OH) 8
  • the coating composition contains as the filming polymer e) an uncrosslinked polymer having one or more glass transition temperatures in the range of -60 ° to + 100 ° C.
  • the glass transition temperatures of the dried polymer film are preferably in the range from -30 ° to + 80 ° C., more preferably in the range from -10 ° to + 60 ° C.
  • the glass transition temperature can be determined by differential scanning calorimetry (DSC, according to ISO 11357-2, heating rate 20 K / min).
  • the molecular weight of the polymer film determined by gel permeation chromatography (GPC), is preferably below 400,000 g / mol.
  • the coating composition preferably comprises as film-forming polymer an emulsion polymer of ethylenically unsaturated monomers such as vinylaromatic monomers, such as ⁇ -methylstyrene, p-methylstyrene, ethylstyrene, tert-butylstyrene, vinylstyrene, vinyltoluene, 1,2-diphenylethylene, 1,1-diphenylethylene, alkenes such as ethylene or propylene, dienes, such as 1, 3-butadiene, 1, 3-pentadiene, 1, 3-hexadiene, 2,3-dimethylbutadiene, isoprene, piperylene or isoprene, ⁇ , ⁇ -unsaturated carboxylic acids, such as acrylic acid and methacrylic acid , their esters, in particular alkyl esters, such as CM 0 - alkyl esters of acrylic acid, in particular the butyl ester, preferably
  • the polymers may optionally contain from 1 to 5% by weight of comonomers, such as (meth) acrylonitrile, (meth) acrylamide, ureido (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, Acrylamidepropanesulfonic acid, methylolacrylamide or the sodium salt of vinylsulfonic acid.
  • comonomers such as (meth) acrylonitrile, (meth) acrylamide, ureido (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, Acrylamidepropanesulfonic acid, methylolacrylamide or the sodium salt of vinylsulfonic acid.
  • the polymer is acrylates verfilmende 4 -Alkylmeth- from one or more of the monomers styrene, butadiene, acrylic acid, methacrylic acid, alkyl acrylates CI_ 4, CI_, composed acrylamide and methacrylamide methylolacrylic.
  • Suitable polymers c) are obtainable, for example, by free-radical emulsion polymerization of ethylenically unsaturated monomers, such as styrene, acrylates or methacrylates, as described in WO 00/50480.
  • the polymers c) are prepared in a manner known per se, for example by emulsion, suspension or dispersion polymerization, preferably in the aqueous phase. It is also possible to prepare the polymer by solution or bulk polymerization, or to disperse it if necessary, and then to disperse the polymer particles in water in a customary manner. In the polymerization, the initiators, emulsifiers or suspending aids customary for the particular polymerization process are used.
  • nanoscale Si0 2 particles d) to be used according to the invention are preferably aqueous, colloidal SiO 2 particle dispersions.
  • the average particle diameter of the Si0 2 particles is in the range of 1 to 200 nm, preferably in the range of 10 to 50 nm.
  • the specific surface of the Si0 2 particles is generally in the range of 10 to 3000 m 2 / g, preferably in the range of 30 to 1000 m 2 / g.
  • the solids content of commercial Si0 2 particle dispersion depends on the particle size and is generally in the range of 10 to 60, preferably in the range of 30 to 50 wt .-%.
  • aqueous, colloidal Si0 2 particle dispersions can be obtained by neutralization of dilute sodium silicates with acids, ion exchange, hydrolysis of silicon compounds, dispersion of fumed silica or gel precipitation.
  • the nanoscale Si0 2 particles to be used according to the invention are known per se and can be present in different forms depending on the production process. For example, suitable dispersions based on silica sol, silica gel, pyrogenic silicas, precipitated silicas or mixtures thereof can be obtained.
  • silica sols are colloidal solutions of amorphous silica in water, also referred to as silica sols or silica sols.
  • the silica is in the form of spherical and surface-hydroxylated particles.
  • the surface of the Si0 2 particles may have a charge which is balanced by corresponding counterions.
  • Alkaline-stabilized silica sols generally have a pH of 7 to 11.5 and may be alkalized, for example, with alkali or nitrogen bases.
  • the silica sols may also be weakly acidic as colloidal solutions.
  • the surface of the brine can be covered with aluminum compounds, for example.
  • the particles can be present both as so-called primary particles and in the form of secondary particles (agglomerates).
  • the mean particle size specified here according to the invention means the mean particle size determined by means of ultracentrifugation and includes the size of primary particles and any agglomerates present therefrom.
  • silicon dioxide dispersions are used in which the Si0 2 particles are present as discrete, uncrosslinked primary particles.
  • the silicone e) to be used according to the invention is preferably an aqueous silicone emulsion.
  • at least one of the following ingredients is included in the silicone emulsion: silicic acid, diethoxyoctylsilyltrimethylsilyl ester, dimethylsiloxane, hydroxy-terminated aminoethylaminopropylsilsesquioxane.
  • an infrared-absorbing pigment such as carbon black, coke, aluminum, graphite or titanium dioxide
  • IR absorber such as carbon black, coke, aluminum, graphite or titanium dioxide
  • the particle size of the IR-absorbing pigment is generally in the range of 0.1 to 100 ⁇ , in particular in the range of 0.5 and 10 ⁇ .
  • the BET surface area is preferably in the range of 10 to 120 m 2 / g.
  • the graphite used is preferably graphite having an average particle size in the range from 1 to 50 ⁇ m.
  • the coating composition flame retardants, such as expanded graphite, borates, in particular zinc borates, in particular ortho-boron phosphate, or intumescent compositions which inflate when exposed to higher temperatures, usually over 80 to 100 ° C, swell, or foam, and a insulating and heat-resistant foam, which protects the underlying insulating foam particles from the effects of fire and heat.
  • flame retardants in the polymer coating it is also possible to achieve adequate fire protection with foam particles containing no, especially no halogenated flame retardants, or to get by with smaller amounts of flame retardants, since the flame retardant concentrated in the polymer coating on the Surface of the foam particles is located and forms a solid scaffolding net when exposed to heat or fire.
  • the coating composition may contain, as additional additives, intumescent compositions containing chemically bound water, or at temperatures above 40 ° C, such as metal hydroxides, metal salt hydrates, and metal oxide hydrates.
  • Suitable metal hydroxides are in particular those of groups 2 (alkaline earth metals) and 13 (boron group) of the Periodic Table. Preferred are magnesium hydroxide, calcium hydroxide, aluminum hydroxide and borax. Particularly preferred is aluminum hydroxide.
  • Suitable metal salt hydrates are all metal salts in whose crystal structure water of crystallization is incorporated.
  • suitable metal oxide hydrates are all metal oxides which contain water of crystallization incorporated into the crystal structure. The number of crystal water molecules per formula unit may be the maximum possible or below, z.
  • copper sulfate pentahydrate trihydrate or monohydrate.
  • the metal salt hydrates or metal oxide hydrates may also contain constitutional water.
  • Preferred metal salt hydrates are the hydrates of metal halides (especially chlorides), sulfates, carbonates, phosphates, nitrates or borates.
  • Suitable examples are magnesium sulfate decahydrate, sodium sulfate decahydrate, copper sulfate pentahydrate, nickel sulfate heptahydrate, cobalt (II) chloride hexahydrate, chromium (III) chloride hexahydrate, sodium carbonate decahydrate, magnesium chloride hexahydrate, and the tin borate. hydrates. Magnesium sulfate decahydrate and tin borate hydrates are particularly preferred.
  • metal salt hydrates are double salts or alums, for example those of the general formula: M 1 M 1 "(SO 4 ) 2 .12H 2 O.
  • M 1 for example, potassium, sodium, rubidium , Cesium, ammonium, thallium or aluminum ions occur as M 1 "act z.
  • aluminum gallium, indium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, rhodium or iridium.
  • metal oxide hydrates z.
  • the coating may additionally be supplemented with other minerals, for example cements, aluminum oxides, vermicullite or perlite. These may be incorporated into the coating composition in the form of aqueous slurries or dispersions. Cements can also be applied by "powdering" on the foam particles. The water necessary for setting the cement can then be supplied with steam during sintering.
  • other minerals for example cements, aluminum oxides, vermicullite or perlite.
  • the amount of the coating composition to be used according to the invention per foam particle is such that per part by weight of foam particles of 1 to 2.3 to 2.3 to 1, in particular from 1 to 1, 7 to 1 to 1 coating composition are used therefore further relates to a process for producing coated foam particles by applying the coating composition according to the invention, preferably in the form of an aqueous dispersion, to the foam particles and optionally drying.
  • the invention relates to a process for producing coated foam particles by i) pre-expanding of expandable styrene polymers into foam particles and ii) applying the combination of a silicate-containing coating, hollow microspheres and optionally nanoscale to be used according to the invention Si0 2 particles, preferably via an aqueous polymer dispersion, on the surface of the foam particles and
  • Expanded polyolefins such as expanded polyethylene (EPE) or expanded polypropylene (EPP) or prefoamed particles of expandable styrene polymers, in particular expandable polystyrene (EPS), can be used as the foam particles.
  • the foam particles generally have a mean particle diameter in the range of 2 to 10 mm.
  • the bulk density of the foam particles is generally 5 to 100 kg / m 3 , preferably 5 to 40 kg / m 3 and in particular 8 to 16 kg / m 3 , determined according to DIN EN ISO 60.
  • the foamed particles based on styrene polymers can be obtained by prefetching EPS with hot air or steam in a prefoamer to the desired density. By prefoaming once or several times in a pressure or continuous prefoamer, final bulk densities of less than 10 g / l can be obtained.
  • expandable styrene polymers containing athermal solids such as carbon black, aluminum, graphite or titanium dioxide, in particular graphite having an average particle size in the range from 1 to 50 ⁇ m particle diameter in amounts of 0.1, are particularly preferably used for the production of insulation boards with high thermal insulation properties to 10 wt .-%, in particular 2 to 8 wt .-%, based on EPS, and are known for example from EP-B 981 574 and EP-B 981 575.
  • the foam particles may contain from 3 to 60% by weight, preferably from 5 to 20% by weight, based on the prefoamed foam particles, of a filler.
  • Suitable fillers are organic and inorganic powders or fibrous materials, as well as mixtures thereof.
  • organic fillers z As wood flour, starch, flax, hemp, ramie, jute, sisal, cotton, cellulose or aramid fibers are used.
  • carbonates, silicates, barite, glass beads, zeolites or metal oxides are used.
  • the mean particle diameter or, in the case of fibrous fillers, the length should be in the range of the cell size or smaller. Preference is given to an average particle diameter in the range from 1 to 100 ⁇ m, preferably in the range from 2 to 50 ⁇ m.
  • inorganic fillers having a density in the range from 1.0 to 4.0 g / cm 3 , in particular in the range from 1.5 to 3.5 g / cm 3 .
  • the whiteness / brightness (DIN / ISO) is preferably 50-100%, in particular 60-98%.
  • the type and amount of fillers can affect the properties of the expandable thermoplastic polymers and the particle foam moldings obtainable therefrom.
  • adhesion promoters such as maleic anhydride-modified styrene copolymers, epoxy group-containing polymers, organosilanes or styrene copolymers with isocyanate or acid groups, can significantly improve the binding of the filler to the polymer matrix and thus the mechanical properties of the particle foam moldings.
  • inorganic fillers reduce flammability.
  • inorganic powders such as aluminum hydroxide, magnesium hydroxide or borax, the fire behavior can be further improved.
  • Such filler-containing foam particles can be obtained, for example, by foaming filler-containing, expandable thermoplastic granules. At high filler contents required for this expandable granules by extrusion blowing agent-containing thermoplastic melts and subsequent pressurized underwater granulation such. As described in WO 2005/056653.
  • the polymer foam particles can additionally be equipped with flame retardants.
  • they may contain from 1 to 6% by weight of an organic bromine compound such as hexabromodylcodecanoate (HBCD) and optionally additionally from 0.1 to 0.5% by weight of dicumyl or a peroxide in the interior of the foam particles or the coating.
  • HBCD hexabromodylcodecanoate
  • dicumyl or a peroxide in the interior of the foam particles or the coating.
  • no halogen-containing flame retardants are used.
  • the coating composition according to the invention is preferably applied to the foam particles in the form of an aqueous polymer dispersion.
  • hydraulic binders may additionally be used Base of cement, lime cement or gypsum are added in amounts where no appreciable embrittlement of the foam occurs.
  • Conventional methods such as spraying, dipping or wetting the foam particles with an aqueous coating composition in conventional mixers, spray devices, dipping devices or drum apparatuses, can be used to coat the foam particles.
  • the foam particles coated according to the invention can additionally be coated with amphiphilic or hydrophobic organic compound.
  • the coating with hydrophobing agent is expediently carried out before the application of the aqueous coating composition according to the invention.
  • hydrophobic organic compounds are, in particular Cio - C 30 - paraffin waxes, reaction products of N-methylolamine and a fatty acid derivatives, reaction products of a Cg-Cn-oxoalkohol with ethylene oxide, propylene oxide or butylene oxide or polyfluoroalkyl (meth) acrylates or mixtures thereof, which can preferably be used in the form of aqueous emulsions.
  • Preferred water repellents are paraffin waxes having 10 to 30 carbon atoms in the carbon chain, which preferably have a melting point between 10 and 70 ° C, in particular between 25 and 60 ° C.
  • paraffin waxes are contained, for example, in the BASF commercial products RAMASIT KGT, PERSISTOL E and PERSISTOL HP, as well as in AVERSIN HY-N from Henkel and CEROL ZN from Sandoz.
  • Another class of suitable hydrophobizing agents are resinous reaction products of an N-methylolamine with a fatty acid derivative, e.g. Example, a fatty acid amide, amine or alcohol, as z.
  • a fatty acid amide, amine or alcohol as z.
  • Their melting point is generally 50 to 90 ° C.
  • Such resins are for. B. in BASF's commercial product PERSISTOL HP included.
  • polyfluoroalkyl (meth) acrylates are suitable, for example Polyperfluoroctylacrylat.
  • This substance is contained in the BASF commercial product PERSISTOL O and in OLEOPHOBOL C from Pfersee.
  • Further suitable coating agents are antistatic agents, such as emulsifier K30 (mixture of secondary sodium alkanesulfonates) or glycerol stearates, such as glycerol monostearate GMS or glycerol tristearate.
  • the method according to the invention is distinguished by the fact that the coating compositions customarily used for the coating of expandable polystyrene, in particular stearates, can be used to a reduced extent or eliminated altogether, without negatively influencing the product quality.
  • the foam particles provided with the coating according to the invention can be sintered in a mold. The coated foam particles can be used while still wet or after drying.
  • the drying of the coating composition applied to the foam particles can take place, for example, in a fluidized bed, paddle dryer or by passing air or nitrogen through a loose bed.
  • a drying time of 5 minutes to 24 hours, preferably 30 to 180 minutes at a temperature in the range of 0 to 80 ° C, preferably in the range of 30 to 60 ° C is sufficient for the formation of the water-insoluble polymer film.
  • the water content of the coated foam particles after drying is preferably in the range from 1 to 40 wt .-%, more preferably in the range of 2 to 30 wt .-%, most preferably in the range of 5 to 15 wt .-%. It can be determined, for example, by Karl Fischer titration of the coated foam particles.
  • the weight ratio of foam particles / coating mixture after drying is preferably 2: 1 to 1:10, particularly preferably 1: 1 to 1: 5.
  • the foam particles dried according to the invention can be sintered in conventional molds with hot air or steam to give foam moldings.
  • the pressure can be generated, for example, by reducing the volume of the mold by means of a movable punch. As a rule, a pressure in the range from 0.5 to 30 kg / cm 2 is set here.
  • the mixture of coated foam particles is filled into the opened mold. After closing the mold, the foam particles are pressed with the stamp, wherein the air between the foam particles escapes and the gusset volume is reduced.
  • the foam particles are connected by the coating to Schaumstoffform body.
  • a compression takes place about 10 to 90%, preferably 60 to 30%, in particular 50 to 30% of the initial volume.
  • a pressure of 1 to 5 bar is usually sufficient for this purpose.
  • the mold is designed according to the desired geometry of the foam molding.
  • the degree of filling depends, inter alia, on the desired thickness of the later molded part.
  • foam boards a simple box-shaped form can be used. Especially with more complicated geometries, it may be necessary be to compact the bed of particles filled in the mold and thus eliminate unwanted voids.
  • the compression can z. B. by shaking the form, tumbling or other suitable measures.
  • hot air or water vapor can be pressed into the mold or the mold heated.
  • any heat transfer media such as oil or steam can be used.
  • the hot air or the mold is suitably tempered for this purpose to a temperature in the range of 20 to 120 ° C, preferably 30 to 90 ° C.
  • the sintering can be carried out continuously or discontinuously under the action of microwave energy.
  • microwaves are generally used in the frequency range between 0.85 and 100 GHz, preferably 0.9 to 10 GHz and irradiation times between 0.1 to 15 minutes. It is also possible to produce foam boards with a thickness of more than 5 cm.
  • the method When using hot air or steam at temperatures in the range of 80 to 150 ° C or by irradiation of microwave energy usually forms an overpressure of 0.1 to 1, 5 bar, so that the method is carried out without external pressure and without volume reduction of the mold can be.
  • the internal pressure resulting from higher temperatures allows the foam particles to expand slightly further, and in addition to bonding via the polymer coating, these can also be welded by softening the foam particles themselves.
  • the gussets disappear between the foam particles.
  • the shape can also be heated with a heat transfer medium as described above. When microwaves are irradiated, the inorganic coating constituents are generally heated, which then crosslink or condense more quickly as a result.
  • the prefoamed and coated foam particles may be continuously applied to the lower of two metal bands, which may optionally have a perforation, and processed with or without compression by the converging metal bands into endless foam sheets.
  • the volume between the two belts is progressively reduced, compressing the product between the belts and eliminating the gussets between the foam particles. After a curing zone, an endless plate is obtained.
  • the volume between the belts can be kept constant and pass through a zone with hot air or microwave irradiation in which the foam particles nachCumen. Again, the gussets disappear and an endless plate is obtained. It is also possible to combine the two continuous process designs.
  • the thickness, length and width of the foam sheets can vary within wide limits and is limited by the size and closing force of the tool.
  • the thickness of the foam sheets is usually 1 to 500 mm, preferably 10 to 300 mm. Further preferred sizes and order ranges are 10 to 200 mm, preferably 20 to 1 10 mm, particularly preferably 25 to 95 mm.
  • the density of the foam moldings according to DIN 53420 is generally 10 to 150 kg / m 3 , preferably 20 to 90 kg / m 3 . With the method it is possible to obtain foam moldings with uniform density over the entire cross section.
  • the density of the edge layers corresponds approximately to the density of the inner regions of the foam molding.
  • crushed foam particles from recycled foam mold bodies can be used.
  • the comminuted foam recycled to 100% or z. B. in proportions of 2 to 90 wt .-%, in particular 5 to 25 wt .-% are used together with virgin material, without significantly affecting the strength and mechanical properties.
  • the coating it is also possible for the coating to add further additives, which preferably make little or no contribution to the combustibility, and / or substances which, in the non-calcined state, have a positive effect on the mechanical or thermal properties, such as vermiculites, for example, for the mechanical and hydraulic properties to modify.
  • the invention therefore furthermore relates to a process for the production of foam moldings characterized by the following steps: a) filling the foam particles coated according to the invention into a mold, pressing the coated foam particles and drying, optionally supported by vacuum and
  • foam particles are used which are additionally coated with an aqueous polymer dispersion, wel when drying in step a) forms a water-insoluble polymer film on the foam particles.
  • the coating compositions according to the invention are suitable for the production of simple or complex foam moldings, such as plates, blocks, tubes, rods, profiles, etc. Preference is given to producing sheets or blocks which can subsequently be sawn or cut into sheets.
  • panels and blocks can be used in building construction to insulate exterior walls. They are particularly preferably used as the core layer for the production of sandwich elements, for example so-called structural insulation panels (SIP), which are used for the construction of cold stores or warehouses.
  • SIP structural insulation panels
  • test A the volume loss in case of fire (fire before)
  • test A the volume loss in case of fire (fire before)
  • a cube with 5 cm edge length is sintered for 15 minutes at 1030 ° C in a muffle furnace.
  • the cube volume is then determined again and subtracted from the initial value ("Volume loss in the fire test before water exposure").
  • test B the water absorption of the cubes is determined.
  • a cube of 5 cm edge length is completely submerged in 50 ° C warm water, the water bath continuously stirred for 24 h and then the cube is dried and weighed again, so as to determine the proportion of leached coating.
  • the water in the container is evaporated and the residue is also weighed so as to check the above-determined Auswaschberg.
  • test C results in the "volume loss in the fire test after water exposure" (fire after) (test C).
  • the fire resistance of the material is tested.
  • the compressive strength according to EN826, the flexural strength according to EN1289 and the lambda value of the hybrid material are measured.
  • a mixture of kaolin (26 g), water glass (1 1 g), Acronal ® S790 dispersion (1 1 g), Wollastonite ® HW 7 (26 g), Betolin ® (34 g), Levasil ® 50 / 50 (34 g), Expancel ® 551WE (2 g), Expancel ® 820SLU (8 g) were recognized.
  • 153 g of this coating mixture was added to 78 g of pre-expanded EPS beads (density 10 g / l) and mixed well.
  • the thus coated spheres were placed in a mold, pressed to 45% of the original volume and the pressed plate heated by contact heat to about 80 ° C, held the temperature for about 2 h, then demolded the plate and until Weight constancy deposited.
  • Example 2 A mixture of kaolin (1347 g), water glass (575 g), Acronal S790 dispersion (575 g), wollastonite HW 7 (1347 g), betolin (1732 g), Levasil 50/50 (1732 g), Expancel 551 WE (97 g), Expancel 820SLU (386 g), deionized water (600g) was used. After complete homogenization, 7790 g of this coating mixture was added to 3970 g of prefoamed EPS beads (density 10 g / l) and mixed well. Subsequently, the thus coated spheres were placed in a mold, pressed to 45% of the original volume and cured the pressed plate by means of microwave radiation. The microwave was driven as follows:

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Abstract

L'invention concerne des particules de mousse revêtues, des procédés pour la production de corps moulés en mousse et l'utilisation de ces derniers.
EP11740682.7A 2010-08-09 2011-08-08 Matériaux stables à hautes températures et à l'humidité présentant des propriétés d'isolation améliorées à base de mousses et de silicates dispersés Withdrawn EP2603550A1 (fr)

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EP11740682.7A EP2603550A1 (fr) 2010-08-09 2011-08-08 Matériaux stables à hautes températures et à l'humidité présentant des propriétés d'isolation améliorées à base de mousses et de silicates dispersés

Applications Claiming Priority (3)

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EP10172268 2010-08-09
EP11740682.7A EP2603550A1 (fr) 2010-08-09 2011-08-08 Matériaux stables à hautes températures et à l'humidité présentant des propriétés d'isolation améliorées à base de mousses et de silicates dispersés
PCT/EP2011/063601 WO2012019988A1 (fr) 2010-08-09 2011-08-08 Matériaux stables à hautes températures et à l'humidité présentant des propriétés d'isolation améliorées à base de mousses et de silicates dispersés

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