WO2013156562A2 - Composition pour une mousse de résine synthétique difficilement inflammable et son procédé de fabrication - Google Patents

Composition pour une mousse de résine synthétique difficilement inflammable et son procédé de fabrication Download PDF

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Publication number
WO2013156562A2
WO2013156562A2 PCT/EP2013/058076 EP2013058076W WO2013156562A2 WO 2013156562 A2 WO2013156562 A2 WO 2013156562A2 EP 2013058076 W EP2013058076 W EP 2013058076W WO 2013156562 A2 WO2013156562 A2 WO 2013156562A2
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Prior art keywords
component
resin
foam
mixture
filler
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PCT/EP2013/058076
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German (de)
English (en)
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WO2013156562A3 (fr
Inventor
Klaus Menke
Volker Gettwert
Sebastian Fischer
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Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e. V.
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Publication of WO2013156562A2 publication Critical patent/WO2013156562A2/fr
Publication of WO2013156562A3 publication Critical patent/WO2013156562A3/fr

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    • 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
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • 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
    • C08J9/0014—Use of organic additives
    • C08J9/0028—Use of organic additives containing nitrogen
    • 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
    • C08J9/0014—Use of organic additives
    • C08J9/0038—Use of organic additives containing phosphorus
    • 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
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
    • C08J9/0066—Use of inorganic compounding ingredients
    • 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
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • 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
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing 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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/026—Crosslinking before of after foaming
    • 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
    • C08J2201/03—Extrusion of the foamable blend
    • 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
    • C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08J2361/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with monohydric phenols
    • C08J2361/10—Phenol-formaldehyde condensates
    • 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
    • C08J2361/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08J2361/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C08J2361/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
    • 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
    • C08J2361/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08J2361/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08J2361/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine

Definitions

  • composition for a flame retardant synthetic resin foam and method for its production
  • the present invention relates to a composition for a flame retardant synthetic resin foam comprising resin component (A), hardener component (B) and
  • the composition relates to a resin component (A) comprising a synthetic resin selected from the group consisting of phenol resin, melamine resin, urea resin or mixtures thereof, a hardener component (B) comprising a reaction product of an organic nitrogen base and a polyol phosphoric acid ester, in particular an oligomeric melamine polyol-organophosphate.
  • a resin component (A) comprising a synthetic resin selected from the group consisting of phenol resin, melamine resin, urea resin or mixtures thereof
  • a hardener component (B) comprising a reaction product of an organic nitrogen base and a polyol phosphoric acid ester, in particular an oligomeric melamine polyol-organophosphate.
  • the hardener component (B) in addition to the
  • the filler component (C) preferably comprises inorganic fillers, in particular water-containing and / or hydroxyl-containing inorganic fillers.
  • the present invention relates to a process for producing a flame-retardant synthetic resin foam, comprising the following process steps:
  • the mixture of resin component (A), filler component (C) and blowing agent component (D) and the hardener component (B) are expelled with an external compressed gas, in particular an inert external compressed gas.
  • an external compressed gas in particular an inert external compressed gas.
  • Propellant component (D) dissolved, based on the weight of the mixture of
  • synthetic resin foams which are flame retardant or nonflammable, in particular synthetic resin foams which do not smolder and are not toxic
  • Phenol resin foams of high filler content are known in the prior art which are hardly inflammable.
  • DE 27 17 775 Al describes a heat-resistant
  • Phenol resin foam containing as filler anhydrous borax Phenol resin foam containing as filler anhydrous borax.
  • US 4,681,902A describes a phenolaldehyde foam with a flame retardant from a mixture of
  • halogen-substituted diphenyl oxide and an organic phosphate or phosphonate in particular pentabromophenyloxide and cresyl diphenyl phosphite.
  • DE 28 25 295 describes a non-combustible material based on phenolic resin and furiuryl alcohol, which does not develop toxic fumes.
  • the material is characterized in particular by a high proportion of inorganic fillers and other additives and contains 62- 76 wt .-% alumina and / or aluminum hydroxide, 12-16 wt .-% phenolic resin, 11.5- 17.5 wt.
  • DE 3407512 C1 describes an improved filler system for a nonflammable Rigid foam of phenolic and furan resin and its use as a building material, wherein the weight ratio of resin to filler in a range of 1: 2.5 to 1: 3.2 and the filler is 40-55 wt .-% aluminum hydroxide, 10-20 Wt% Boric acid, 2-5 wt%
  • phenolic foams tend to be retarded due to oxidation processes on the surface of the charred phenolic foams. Afterglow is the phenomenon of continued glowing and burning without a visible flame. Therefore, the known phenolic foams do not meet the requirements for classification into the building material classes Bl according to DIN 4102-1. Large amounts of inorganic fillers are added, usually more than 50% by weight to the thermal
  • Object of the present invention is to provide a composition for a
  • polyurethane-based foams tend to foam, so that the volume after expanding into a foam continues to change over a certain period of time, in particular increases. This is particularly disadvantageous in an application of the polyurethane foam as mounting foam in the construction sector.
  • a synthetic resin in particular a synthetic resin selected from the group consisting of phenolic resin, melamine resin, urea resin or mixtures thereof to a synthetic resin foam without the volume after extrusion from the pressure vessel continues to change, in particular increases, so that the expanded synthetic resin can be used advantageously as a mounting foam in the construction sector.
  • the present invention relates to a composition for a flame retardant resin foam comprising a resin component (A), a hardener component (B) and a filler component (C).
  • a composition for a flame retardant resin foam comprising a resin component (A), a hardener component (B) and a filler component (C).
  • composition according to the invention in one embodiment of the composition according to the invention, the
  • Resin component (A) a phenolic resin.
  • the phenolic resin is the only synthetic resin in the resin component (A).
  • flame retardant substances which do not ignite in contact with open fire, sparks or embers, and, if ignited, do not continue to burn, but extinguished by itself.
  • flame retardant is to be understood as meaning a substance which is covered by the fire classification B1 according to DIN 4102.
  • phenolic resin is to be understood as meaning a polycondensation product of phenol and aldehyde. Suitable phenolic resins are not critical
  • Restrictions are well known to those skilled in the art. They are obtained by the condensation of phenol with aldehyde in an alkaline or acidic medium. When alkaline condensing agents are used, viscous, low molecular weight resins are formed, also referred to as resoles. Resoles are fusible, soluble phenoplasts containing reactive methylol groups. The benzene rings are connected to each other via methylene groups and via ether bridges. Resoles are self-curing and do not have a long shelf life. It is known that the storage stability of
  • Resoles can be improved by etherification with alcohols. It is also known that resoles cure in the presence of an acidic catalyst at elevated temperatures become. When using acid condensation agents, novolacs are formed.
  • Novolaks are phenolic resins with a ratio of aldehyde to phenol less than 1.
  • the benzene rings are hereby mainly linked together via methylene groups.
  • Novolaks are only weakly cross-linked and therefore thermoplastic. Novolaks are soluble in organic solvents or resoles. Novolacs can be hardened into infusible phenoplasts.
  • the resin component (A) comprises a phenolic resin, ie a condensation product of phenol and at least one aldehyde.
  • the aldehyde is preferably a CpCg alkylaldehyde or a mixture of CpCg Alkylaldehyden, in particular formaldehyde or a mixture of formaldehyde and at least one other CpCg alkylaldehyde.
  • formaldehyde is the only aldehyde in the phenolic resin of the resin component (A).
  • the resin component (A) comprises a liquid phenolic resin prepolymer. By prepolymer is meant a monomer or mixture of monomers which are too intermediate
  • the phenolic resin of the resin component (A) comprises resol.
  • resole is the only phenolic resin in the
  • Resin component (A) in particular the only synthetic resin in the resin component (A).
  • the resin component (A) comprises a mixture of phenolic resin and melamine resin.
  • the mixture is
  • Phenolic resin and melamine resin the only resin in the resin component (A).
  • melamine resin is meant a polycondensation product of melamine and aldehyde.
  • the melamine resins useful in the invention are not subject to any critical limitations and are well known to those skilled in the art. They are obtained by the condensation of melamine with aldehyde.
  • the aldehyde is preferably a CpCg alkylaldehyde or a mixture of CpCg Alkylaldehyden, in particular
  • Formaldehyde or a mixture of formaldehyde and at least one other CpCg alkylaldehyde is the only aldehyde in the melamine resin of the resin component (A).
  • the composition for the flame retardant synthetic resin foam further comprises a hardener component (B).
  • a reactive resin composition whose viscosity increases is obtained. Curing in the context of this invention means the transfer of a plastically deformable resin into a hard and infusible plastic, in particular the transfer of a liquid or solid but fusible resin into an infusible plastic.
  • the curing takes place via polyaddition, polycondensation or polymerization mechanisms after the addition of at least one hardener.
  • Hardeners can be catalytically active or reactive, polyfunctional compounds. However, hardening can also be caused by other influences, such as the influence of components from the environment or radiation.
  • the hardener component comprises (B) at least compounds having a pH ⁇ 7. It comes in the resin selected from the group consisting of phenolic resin, melamine resin, urea resin or mixtures thereof, via a polycondensation reaction to a strong crosslinking , where a
  • the hardener component (B) comprises at least one sulfonic acid derivative, such as alkylsulfonic acid or arylsulfonic acid, in particular C 1 -C 30 -alkylbenzenesulfonic acid.
  • the hardener component (B) furthermore comprises at least one reaction product of an organic nitrogen base and a polyol phosphoric acid ester, in particular a reaction product of melamine and polyol Phosphoric acid esters such as an oligomeric melamine-polyol phosphoric acid ester.
  • the hardener component (B) comprises in addition to the reaction product of an organic nitrogen base and a polyol phosphoric acid ester at least one further organic or inorganic acid, in particular at least one further acid selected from the group consisting of alkylsulfonic acid, arylsulfonic acid, phosphoric acid, polyphosphoric acid , acidic organic phosphates, alkylphosphinic acid, arylphosphinic acid, alkylphosphonic acid,
  • Arylphosphonic acid or mixtures thereof Arylphosphonic acid or mixtures thereof.
  • the organic or inorganic acids used in the hardener component (B) in addition to the reaction product of an organic nitrogen base and a polyol-phosphoric acid ester serve to control the hardening reaction, in particular the acceleration of the hardening reaction.
  • the hardener component (B) comprises, in addition to the reaction product of an organic nitrogen base and a polyol phosphoric acid ester, at least one further organic acid, in particular
  • reaction product of an organic nitrogen base and a polyol-phosphoric acid ester is the only compounds having a pH of ⁇ 7 in the hardener component (B).
  • polyol phosphoric esters described in the context of the invention are not subject to any critical restrictions and are well known to the person skilled in the art.
  • Polyol-phosphoric acid esters are described in WO 99/05200 and can be obtained by a reaction of aryl or alkyl halophosphates, in particular diaryl or dialkyl halophosphates with an alcohol, in particular a polyhydric alcohol.
  • the reaction of the polyol phosphoric acid ester with the organic nitrogen base takes place in the presence of a Aldehyds, so that a condensation product or a polycondensation product is formed.
  • the reaction of the polyol-phosphoric esters with organic nitrogen bases in the presence of an aldehyde is known to the person skilled in the art and is described in DE 10112155.
  • the hardener component (B) comprises at least one oligomeric melamine-polyol phosphoric acid ester which is obtained by reacting melamine and polyol phosphoric acid in the presence of an aldehyde, in particular formaldehyde.
  • condensation products with increased thermal stability are obtained by reacting organic nitrogen bases and polyol phosphoric esters in the presence of aldehydes.
  • the condensation products obtained in this way are used in the prior art as intumescent coating or coating compositions.
  • Intumescent paints or coatings foam under thermal stress and form an "insulating" protective layer in the form of a foam. The swelling of the material prevents heating or inflammation of the material
  • condensation products from the reaction of organic nitrogen bases and polyol phosphoric esters in the presence of aldehydes are suitable for improving the resistance of synthetic resin foams to thermal stress in the event of fire in particular the resistance of synthetic resin foams comprising a synthetic resin selected from the group consisting of phenolic resin, melamine resin, urea resin or mixtures thereof.
  • aldehydes in particular oligomeric melamine-polyol phosphoric esters
  • the hardener component (B) of the composition according to the invention therefore comprises oligomeric melamine-polyol-phosphoric acid esters.
  • the oligomeric melamine-polyol phosphoric acid ester forms with the remaining coating ingredients, e.g. the binder in heat or
  • Fire action is an insulating foam that protects the substrate from the heat protects or inflammable materials that delay the inflammation. There is no foaming in the present invention.
  • the afterglow of the phenolic foam is suppressed by acting directly on the decomposition of the phenolic resin and the production of suffocating and fire-extinguishing gases such as nitrogen, water vapor and carbon dioxide.
  • the oligomeric melamine-polyol phosphoric acid ester forms an inner barrier layer when exposed to heat in the phenolic resin foam, which closes the pores of the phenolic foam and thus prevents diffusion of oxygen into the interior, which significantly contributes to suppressing afterglow.
  • the filler component (C) of the composition according to the invention comprises inorganic fillers, in particular water-containing and / or hydroxyl-containing inorganic fillers. Crystal water-containing and / or hydroxyl-containing inorganic fillers have the advantage that water can be released when exposed to thermal stress. This has a positive influence on the thermal resistance of the synthetic resin foams formed from the composition according to the invention.
  • the filler component (C) comprises inorganic fillers containing water of crystallization and / or hydroxyl groups, preferably alkaline earth sulfates, more preferably silicates, in particular water-containing zeolites.
  • the filler component (C) consists of CaSÜ 4 , with a mean particle size distribution ⁇ 50 ⁇ and a absolute grain size of 98% ⁇ 100 ⁇ .
  • Embodiment of the invention consists of the filler component (C) of CaSÜ 4 * 2 H 2 0, with an average particle size distribution ⁇ 50 ⁇ and an absolute particle size of 98% ⁇ 100 ⁇
  • the composition according to the invention also comprises a blowing agent component (D) with at least a propellant.
  • blowing agents are to be understood as substances for foaming synthetic and synthetic materials Building materials are used and under the action of heat or chemicals
  • blowing agent for the purpose of the invention, any inert organic compound which is volatile in a range of -20 ° C to 100 ° C at atmospheric pressure can be used.
  • suitable blowing agents are hydrocarbons, oxygen derivatives of hydrocarbons,
  • Halogenated hydrocarbons in particular alkanes, alkyl ethers and / or halogenated derivatives.
  • the composition of the present invention comprises, in addition to the resin component (A), the hardener component (B) and the filler component (C), a blowing agent component (D) which is halogenated or halogenated depending on whether the composition is to be expanded to open-cell or closed-cell plastic contains non-halogenated blowing agent.
  • a blowing agent component D which is halogenated or halogenated depending on whether the composition is to be expanded to open-cell or closed-cell plastic contains non-halogenated blowing agent.
  • the inventive composition comprises a
  • Propellant component (D) with a propellant which has a boiling point ⁇ 35 ° C at atmospheric pressure in particular propellant selected from the group consisting of butane, isobutane, pentane, isopentane and cyclopentane or mixtures thereof.
  • composition according to the invention comprises, in addition to resin component (A), hardener component (B) and filler component (C) none
  • Blowing agent component (D) It has surprisingly been found that the composition according to the invention can also be foamed without the addition of a blowing agent component (D).
  • the reaction enthalpy released in the reaction between resin component (A) and hardener component (B) causes the release of volatile constituents of the composition, so that the invention
  • composition can be foamed without the addition of a separate blowing agent component (D).
  • the composition according to the invention is characterized in that the thermal capacity of a synthetic resin foam obtained therefrom, in particular a synthetic resin foam derived therefrom, is selected from the group consisting of
  • the proportion of inorganic fillers is preferably ⁇ 50% by weight. More preferably, the proportion of inorganic fillers in the range of 1-50 wt .-%, even more preferably in the range of 10-50 wt .-%, for example, 20-50 wt .-%.
  • composition for a flame retardant synthetic resin foam contains the following components:
  • resin component (A) comprising at least one synthetic resin
  • phenolic resin selected from the group consisting of phenolic resin, melamine resin, urea resin or mixtures thereof, in particular phenolic resin or a mixture of
  • Phenolic resin and melamine resin Phenolic resin and melamine resin
  • hardener component (B) containing at least one reaction product of an organic nitrogen base and a polyol phosphoric acid ester, in particular an oligomeric melamine-polyol phosphoric acid ester.
  • filler component (C) 1-50 wt .-% filler component (C), comprising at least one inorganic filler, in particular a water of crystallization and / or
  • hydroxyl-containing inorganic filler preferably finely ground calcium sulfate 2H 2 0.
  • blowing agent component (D) comprising at least one blowing agent which has a boiling point ⁇ 35 ° C at atmospheric pressure, in particular propane, butane, isobutane, pentane, isopentane and cyclopentane and mixtures thereof.
  • the hardener component (B) comprises a
  • Reaction product of an organic nitrogen base and a polyol-phosphoric acid ester in particular an oligomeric melamine-polyol-phosphoric acid ester.
  • the reaction product is an organic
  • Nitrogen base and a polyol-phosphoric acid ester is the only constituent of Hardener component (B).
  • the reaction product of an organic nitrogen base and a polyol phosphoric acid ester, in particular an oligomeric melamine-polyol phosphoric acid ester with at least one other organic and / or inorganic acid is used, in particular with at least one other organic and / or inorganic acid selected from the group consisting of alkyl or arylsulfonic acids, phosphoric acids, polyphosphoric acids, acidic organic
  • the hardener component (B) comprises, in addition to the reaction product of an organic nitrogen base and a polyol phosphoric acid ester, at least one further organic acid, in particular
  • the invention also relates to a process for producing a flame-retardant synthetic resin foam, in particular for producing a synthetic resin foam selected from the group consisting of phenolic resin foam, melamine resin foam, urea foam or mixtures thereof, comprising the following process steps:
  • the blowing agent component (D) is, according to a preferred embodiment, dissolved in a dispersed mixture of resin component (A) and filler component (C).
  • the inventive method is characterized in that the resin component (A) is not expanded during extrusion, but is prefoamed in a pressure vessel and extruded in the already foamed state from the pressure vessel.
  • the mixture of resin component (A), filler component (C) and blowing agent component (D), and the hardener component (B) with the aid of an external pressure gas, in particular an inert compressed gas such as nitrogen or argon extruded (expelled).
  • the propellant is only for pre-foaming, preferably only for
  • Foam systems also for extruding from the pressure vessel.
  • about 20-40% by weight of blowing agent are dissolved in the formulation to be foamed, less than 20% by weight are dissolved in the process according to the invention.
  • ⁇ 20% by weight of blowing agent component (D) is dissolved in the resin component (A), preferably ⁇ 10% by weight, more preferably ⁇ 5% by weight, in particular ⁇ 3% by weight, based on the weight the resin component (A). Due to the low blowing agent content in the formulation to be foamed, no post-expansion during extrusion is observed.
  • the blowing agent content is so low that it is sufficient only for foaming the resin component (A) in the pressure vessel and does not foam after extrusion. In one embodiment, it is extruded in a temperature range of 15-60 ° C. In a particular embodiment, the flow viscosity of the resin component (A) and the hardener component (B) are adjusted by admixing a fumed silica.
  • compositions for flame-retardant synthetic resin foams in particular fast-curing polyurethane foams tend to foam strongly after being extruded from the pressure vessel, so that the volume of the synthetic resin foam continues to change over a certain period of time, in particular increases or due to low stability of the synthetic resin foam shrinks.
  • polyurethane foams in the construction industry is widespread, in particular
  • compositions for phenol resin foams, melamine resin foams, urea foams or mixtures thereof are only hardened much more slowly and form much more labile foams compared to polyurethane, so that they are not suitable for many applications in the building industry, such as assembly foams.
  • the process according to the invention makes it possible to produce a flame-retardant synthetic resin foam, in particular a phenolic resin foam, melamine resin foam,
  • Urea foam or mixtures thereof without the resin extruded from the pressure vessel foams much or shrinks due to the low stability of the synthetic resin foam.
  • a suitable hardener component (B) the speed of the curing reaction of the composition according to the invention can be adjusted.
  • a mixture of organic and / or inorganic acids is used, which causes a high speed of the curing reaction, so that an application in the construction sector, in particular as a mounting foam is possible.
  • At least one further organic and / or inorganic acid in addition to the reaction product of an organic nitrogen base and a polyol phosphoric acid ester, at least one further organic and / or inorganic acid, in particular at least one further organic and / or inorganic acid selected from the group consisting of alkyl or arylsulfonic acids , Phosphoric acids,
  • Polyphosphoric acids acidic organic phosphates, alkylphosphinic acids,
  • Arylphosphinic acids alkylphosphonic acids, arylphosphonic acids or mixtures thereof.
  • the other organic and inorganic acids preferred within the scope of this invention may readily be used.
  • the mixture of resin component (A), filler component (C) and blowing agent component (D) and the hardener component (B) extruded from separate pressure vessels, so that the mixture and the hardener component (B) are mixed only directly in the concrete application, in particular by a static mixer or a specially designed mixing head.
  • the method according to the invention comprises at least one
  • Pressure vessel in particular at least two pressure vessels, wherein resin component (A) and hardener component (B) are kept in stock separately from each other.
  • the inventive method comprises two pressure vessels, wherein the resin component (A) is prefoamed in a first pressure vessel with the blowing agent component (D) and the hardener component (B) is present in a second pressure vessel.
  • the present invention relates to a composition for a flame-retardant synthetic resin foam comprising a resin component (A), a hardener component (B) and a filler component (C).
  • the composition of the invention for a flame-retardant synthetic resin foam may also contain a blowing agent component (D) and other additives.
  • the composition of the invention comprises a resin component (A) selected from the group consisting of phenolic resin, melamine resin, urea resin, alkyd resin, epoxy resin, polyester resin, polyurethane resin, polyamide resin, vinyl ester resin or mixtures thereof, preferably phenolic resin, melamine resin, urea resin or mixtures thereof, in particular a mixture made of phenolic resin and melamine resin.
  • composition according to the invention in one embodiment of the composition according to the invention, the
  • Resin component (A) Phenolic resin.
  • the phenol resin is the only resin in the resin component (A).
  • the phenolic resin is a condensation product of phenol and at least one aldehyde.
  • the aldehyde is preferably a Ci-Cg alkylaldehyde or a mixture of Ci-Cg alkyl aldehydes, especially formaldehyde or a mixture of formaldehyde and at least one other CpCg alkylaldehyde.
  • formaldehyde is the only aldehyde in the phenolic resin of the resin component (A).
  • the resin component (A) comprises a mixture of phenolic resin and melamine resin.
  • the mixture is
  • Phenolic resin and melamine resin the only resin in the resin component (A).
  • Melamine resins are obtained by the condensation of melamine with aldehyde.
  • the aldehyde is preferably a Ci-Cg alkylaldehyde or a mixture of Ci-Cg alkyl aldehydes, especially formaldehyde or a mixture of formaldehyde and at least one further Ci-Cg alkylaldehyde.
  • formaldehyde is the only aldehyde in the melamine resin of the resin component (A).
  • the resin component (A) comprises 1 to 99% by weight of phenolic resin and 1 to 99% by weight of melamine resin, preferably 40 to 95% by weight of phenolic resin and 5 to 60% by weight of melamine resin, further preferred 45-90 wt .-% phenolic resin and 10-55 wt .-% melamine resin, more preferably 60- 90 wt .-% phenolic resin and 10-40 wt .-%, more preferably 70-90 wt .-% phenolic resin and 10-30% by weight of melamine resin, in particular 80-90% by weight of phenolic resin and 10-20% by weight of melamine resin.
  • the phenolic resin and the melamine resin are mixed in a ratio such that, including the additives, in particular the cell-forming and stabilizing additives, a total of 100% by weight results.
  • the resin component (A) comprises a mixture of phenolic resin and urea resin.
  • the mixture is
  • Phenolic resin and urea resin the only resin in the resin component (A).
  • Urea resins are obtained by the condensation of urea with aldehyde.
  • the aldehyde is preferably a Ci-Cg alkylaldehyde or a mixture of Ci-Cg alkyl aldehydes, especially formaldehyde or a mixture of formaldehyde and at least one other CpCg alkylaldehyde.
  • Formaldehyde is the only aldehyde in the urea resin of the resin component (A).
  • the resin component (A) comprises 5-95% by weight of phenolic resin and 5-95% by weight of urea resin, preferably 40-95% by weight of phenolic resin and 5-60% by weight of urea resin.
  • phenolic resin and the urea resin are mixed in a ratio such that, including the additives, in particular the cell-forming and stabilizing additives, a total of 100% by weight results.
  • the resin component (A) comprises a mixture of phenolic resin, melamine resin and urea resin.
  • the mixture of phenolic resin, melamine resin and urea resin is the only synthetic resin in the resin component (A).
  • the resin component comprises (A) 5-95 wt .-% phenolic resin, 1-95 wt .-% melamine resin and 1-95 wt .-% urea resin, preferably 40-90 wt .-% phenolic resin and 5-60% by weight of melamine resin and 5-60% by weight of urea resin, more preferably 50-90% by weight
  • Phenolic resin 5-50% by weight of melamine resin and 5-50% by weight of urea resin, more preferably 60-90% by weight of phenolic resin, 5-40% by weight of melamine resin and 5-40% by weight of urea resin preferably 70-90% by weight of phenolic resin, 5-30% by weight of melamine resin and 5-30% by weight of urea resin, in particular 80-90% by weight of phenolic resin, 5-20% by weight of melamine resin and 5-20 % By weight urea resin.
  • the phenolic resin, the melamine resin and the urea resin are mixed in a ratio such that, including the additives, in particular the cell-forming and stabilizing additives, a total of 100% by weight results.
  • the phenolic resin comprises
  • Resin Component (A) Resol is the only phenolic resin in the resin component (A).
  • the composition for the flame retardant synthetic resin foam further comprises a hardener component (B).
  • the hardener component (B) comprises at least one compound having a pH ⁇ 7, in particular a catalytically active compound having a pH ⁇ 7.
  • the hardener component (B) comprises at least one organic acid, in particular at least one organic acid selected from the group consisting of C 1 -C 2 0 alkyl sulfonic acid, C 1 -C 2 0 aryl sulfonic acid, C 8 -C 30 alkyl benzene sulfonic acid, partial phosphoric acid esters, organic Phosphinic acid, organic phosphonic acids or mixtures thereof, preferably an organic acid selected from the group consisting of / jara-toluenesulfonic acid, benzenesulfonic acid, dodecylsulfonic acid,
  • Tetrapropylenebenzenesulfonic acid partial acidic phosphoric acid esters, alkylphosphinic acid, arylphosphinic acid, alkylphosphonic acid, arylphosphonic acids or mixtures thereof. It is also possible to use corresponding C 1 -C 2 0 alkyl sulfonates, C 1 -C 2 0 aryl sulfonates, C 1 -C30 alkyl benzene sulfonates. In a further embodiment, the
  • Hardener component (B) an inorganic acid, in particular an inorganic acid selected from the group consisting of, sulfuric acid, phosphoric acid,
  • the curative component (B) comprises at least one organic acid and at least one further acid, in particular at least one organic acid selected from the group consisting of C 1 -C 20 alkyl sulfonic acid, C 1 -C 20 arylsulfonic acid, C1 -C30 alkylbenzene sulfonic acid or mixtures thereof and at least one further acid selected from the group consisting of sulfuric acid, phosphoric acid,
  • Polyphosphoric acid alkyl or aryl substituted phosphine or phosphonic acids or mixtures thereof.
  • this includes the hardener component (B)
  • reaction product of an organic nitrogen base and a polyol-phosphoric acid ester in particular an oligomeric melamine-polyol-phosphoric acid ester.
  • the reaction product of an organic nitrogen base and a polyol-phosphoric acid ester are the only compounds having a pH ⁇ 7 in the hardener component (B). It is possible that the reaction product of an organic nitrogen base and a polyol-phosphoric acid ester, in particular an oligomeric melamine-polyol-phosphoric acid ester is the only constituent of the
  • Hardener component (B) is.
  • the hardener component (B) is.
  • Hardener component (B) in addition to the reaction product of an organic nitrogen base and a polyol-phosphoric acid ester at least one further organic and / or inorganic acid, in particular at least one further organic acid selected from the group consisting of alkyl or arylsulfonic acids, phosphoric acids, polyphosphoric acids, acidic organic Phosphates, alkylphosphinic acids,
  • Arylphosphinic acids alkylphosphonic acids, arylphosphonic acids or mixtures thereof, in particular alkylsulfonic acid and / or arylsulfonic acid.
  • reaction product of an organic nitrogen base and a polyol-phosphoric acid ester is used with at least one further acid in a ratio of 1: 4 to 4: 1, preferably with at least one further acid in a ratio of 2: 1 to 4 : 1.
  • Reaction product of an organic nitrogen base and a polyol used phosphoric acid esters are preferably selected from the group consisting of alkyl or arylsulfonic acids, phosphoric acids, polyphosphoric acids, acidic organic phosphates, alkylphosphinic, arylphosphinic, alkylphosphonic, arylphosphonic or mixtures thereof.
  • alkyl or arylsulfonic acids phosphoric acids
  • polyphosphoric acids polyphosphoric acids
  • acidic organic phosphates alkylphosphinic, arylphosphinic, alkylphosphonic, arylphosphonic or mixtures thereof.
  • the other organic and inorganic acids preferred within the scope of this invention may readily be used.
  • the hardener component (B) comprises, in addition to the reaction product, an organic nitrogen base and a polyol phosphoric acid ester and at least one further organic or inorganic acid at least one further acid selected from the group consisting of phosphoric acid, polyphosphoric acid, acidic organic phosphates, alkylphosphinic acid, arylphosphinic acid, alkylphosphonic acid, arylphosphonic acid or mixtures thereof.
  • the other organic and inorganic acids preferred within the scope of this invention may readily be used.
  • the organic nitrogen base is preferably selected from the group consisting of melamine, polyvinylamine, methylenediamine, guanidine, methylolmelamine, 1,3,4,6,7,9,9b-heptaazaphenalene-2,5,8-triamine, pyrimidine-2,4 , 6-triamine, phenyl-1, 2,4-triamine, 1,2,4-triazole-3,4,5-triamine, 4H-l, 2,4-triazole-3,4,5-triamine, 2 , 4,6-triamino-5-pyrimidinylamine, tris-3-aminopropylamine triethylenetetramine, 6-phenyl-1, 3,5-triazine-2,4-diamine,
  • a melamine-formaldehyde resin prepolymer is used, in particular an alkyl- or aryl-substituted melamine-formaldehyde resin prepolymer.
  • Polyol-phosphoric esters used in the invention are not subject to any critical limitations and are well known to those skilled in the art.
  • Polyol-phosphoric acid esters may be obtained by a reaction of aryl or alkyl halophosphates, especially diaryl or dialkyl halophosphates, with an alcohol, especially a polyalcohol.
  • oligomeric polyol-phosphoric esters are used for the reaction with the organic nitrogen base, in particular polyol-phosphoric acid esters with polyols selected from the group consisting of 1,2-ethanediol, 1,2- or 1,3-propanediol, 1 , 2-, 1,3-, 1,4- or 2,3-butanediol, glycerol, trimethylolmethane, trimethylolethane, trimethylolpropane, neopentyl glycol, pentaerythritol, dipentaerythritols, polypentaerythritols, pentitols, hexitols, pentositols, 2,3-dimethylol-1, 3-dihydroxybenzene or mixtures thereof, in particular pentaerythritol or sorbitol.
  • polyol-phosphoric acid esters with polyols selected from the group consisting of 1,2-
  • the reaction of the polyol-phosphoric acid ester with the organic Nitrogen base takes place in the presence of an aldehyde, so that a polycondensation product is formed.
  • the polycondensation products in particular the polycondensation products of melamine and polyol phosphoric acid in the presence of formaldehyde show increased thermal stability and greatly reduced solubility in water, without suffering the known flame retardancy.
  • the hardener component (B) comprises at least one oligomeric melamine-polyol-phosphoric acid ester which is prepared by reacting melamine and polyol phosphoric acid in the presence of an aldehyde, in particular
  • Formaldehyde is obtained.
  • the oligomeric melamine-polyol-phosphoric acid ester have a charring effect on the resins.
  • an inner barrier layer is formed in the phenolic resin foam, and the glow of the phenolic resin can be suppressed.
  • a foam formed therefrom, in particular a phenolic resin foam formed therefrom, which contains a product obtained from the reaction of melamine resin or urea resin with the polyol phosphoric acid ester can thus be classified in the fire shaft test according to DIN 4102 in the building material class Bl.
  • Compositions formed therefrom are also useful as binders for fiber insulation, especially acoustic and thermal insulation panels to prevent afterglow caused by the oxidation of the carbon formed by carbonization in case of fire.
  • compositions for flame-retardant synthetic resin foams advantageously have the properties described
  • Phosphoric acid esters in the presence of aldehydes include, in particular, oligomeric melamine-polyol phosphoric acid esters.
  • the synthetic resin foams prepared in the presence of these polycondensation products preferably synthetic resin foams selected from a group consisting of phenolic resin foam, melamine resin foam, urea resin foam or mixtures thereof, in particular melamine-phenolic resin foam, show increased thermal resistance and greatly improved afterglow behavior. It has surprisingly been found that the formation of an insulating layer caused fire protection effect is achieved not only in the form of a coating or paint, but also when the polycondensate is dispersed in the synthetic resin foam.
  • the hardener component (B) comprises the
  • inventive composition therefore oligomeric melamine-polyol phosphoric acid ester.
  • Oligomeric melamine-polyol-phosphoric acid esters have hitherto been used only in intumescent fire-protection coatings and are unknown as a hardener component in phenolic resin foams. Oligomeric melamine-polyol-phosphoric acid esters assisted in the charring and barrier action of the foam in case of fire.
  • Resin composition by varying ratios to different formulations and applications adapt.
  • the oligomeric melamine-polyol phosphoric acid ester forms with the remaining coating ingredients, e.g. When exposed to heat or fire, the binder releases an insulating foam that protects the substrate from heat or flammable materials that delay the ignition process. There is no foaming in the present invention. Due to the charring acting on the phenol resin property together with the formation of non - combustible gases and reaction products, the afterglow of the
  • the filler component (C) of the composition according to the invention comprises inorganic fillers, in particular water-containing and / or hydroxyl-containing inorganic fillers.
  • inorganic fillers in particular water-containing and / or hydroxyl-containing inorganic fillers.
  • water-containing and / or hydroxyl-containing inorganic fillers have the advantage that water can be liberated during a thermal load, which has a positive influence on the thermal stability of the composition of the invention
  • Resin foams has.
  • the fillers contribute to the formation of a firmer carbonized foam and a refractory inorganic layer and promote, when water-containing and / or hydroxyl-containing fillers are used, at the same time the fire protection effect.
  • the filler component (C) comprises inorganic
  • Hydrocarbon and / or Hydroxly phenomenonhaltinge fillers in particular fillers selected from the group consisting of MgS0 4 , CaS0 4 , SrS0 4 , BaS0 4 , Al (OH) 3 bentonites, montmorillonites, zeolites, boehmite, microencapsulated borax and silicates, in particular hydrous zeolites such as naturally occurring phillipsite.
  • the filler component (C) comprises silicates containing water of crystallization and / or hydroxyl groups, in particular water-containing zeolites.
  • fillers having a pH of 6-8 Preference is given to using fillers having a pH of 6-8, since in this way the acid curing of the synthetic resin is not hindered and the stability of the hydroxymethylene-containing phenolic resin is not impaired.
  • the filler component (C) comprises at least one inorganic material containing water of crystallization selected from the group consisting of CaS0 4 , MgS0 4 , CaS0 4 * 2 H 2 0, MgS0 4 * 7 H 2 0 or mixtures thereof.
  • the filler component (C) comprises CaS0 4 , in particular CaS0 4 * 2 H 2 0. In a further embodiment of the invention, the filler component (C) comprises CaS0 4 , in particular CaS0 4 * 2 H 2 0, no further fillers, which results in particularly good results.
  • the composition according to the invention comprises a blowing agent component (D) with at least one blowing agent.
  • any inert organic compound may be used which is volatile in a range of -30 ° C to 100 ° C, preferably in a range of -20 ° C to + 50 ° C, at atmospheric pressure and has a low heat of vaporization.
  • the blowing agent any inert organic compound may be used which is volatile in a range of -30 ° C to 100 ° C, preferably in a range of -20 ° C to + 50 ° C, at atmospheric pressure and has a low heat of vaporization.
  • the blowing agent any inert organic compound which is volatile in a range of -30 ° C to 100 ° C, preferably in a range of -20 ° C to + 50 ° C, at atmospheric pressure and has a low heat of vaporization.
  • the blowing agent component (D) comprises at least one blowing agent having a boiling point at atmospheric pressure ⁇ 60 ° C, preferably ⁇ 40 ° C, more preferably ⁇ 35 ° C, in particular ⁇ 30 ° C.
  • the propellant of the propellant component (D) is selected from the group consisting of propane, butane, isobutane, pentane, isopentane, cyclopentane, 1,1,1,3,3-pentafluorobutane, 1,1,2,2,3 , 3,4,4-octafluorobutane, 1,1,1,2,2,3,3,4,4,4-decafluoropentane, 1,1,2,2,3,4,5,5,5 Decafluoropentane, 1,2,3,3,4,4,5,5-octafluorocyclopentane or mixtures thereof.
  • the blowing agent of the blowing agent component (D) is preferably selected from the group consisting of propane, n-pentane, butane, isobutane, isopentane, cyclopentane or mixtures thereof, in particular isobutane.
  • the blowing agent is preferably selected from the group consisting of propane, isobutane, butane, n-pentane or mixtures thereof, in particular isobutane
  • the composition according to the invention comprises 0.5 to less than 20% by weight of blowing agent component (D), preferably 0.5 to 15% by weight, more preferably 0.5 to 10% by weight, more preferably 0.5 to 5% by weight, in particular 0.5 - 3 wt .-%, based on the weight of the resin component (A).
  • the composition according to the invention does not comprise a blowing agent component (D). It has surprisingly been found that the composition of the invention can also be foamed without the addition of a blowing agent component (D), since by the released reaction enthalpy in the reaction between the resin component (A) and the hardener component (B) volatiles are released.
  • composition of the invention may also contain other additives, these being either the composition of the invention itself or individual
  • composition according to the invention preferably comprises 0.1-15% by weight of additives, more preferably 0.1-10% by weight, in particular 0.1-5% by weight.
  • additives include, for example, plasticizers, metal salts, pigments, dyes, stabilizers, foam boosters, cell formers, nucleating agents and
  • Wetting agents are used in particular in the production of synthetic resin foams, as this the surface tension of the composition during the production of synthetic resin foams, as this the surface tension of the composition during the production of synthetic resin foams
  • the composition according to the invention comprises additives selected from the group consisting of alkoxysilane, hydroxyalkylene methacrylate, polyethersiloxane, silanized silicon dioxide, alkoxyarylsulfonic acids or mixtures thereof.
  • the composition comprises the additives
  • Tegostab 8404 Aluminum hydroxide, Tegostab 8404, Kraton L 1253, Aerosil R972 no further additives used.
  • Tegostab 8404, Kraton L 1253, Aerosil R972 are names for commercial products.
  • Tegostab 8404, a liquid short chain polyether siloxane, and Kraton L 1253, an oligomeric polyethylene / butylene hydroxymethacrylate, are the already mentioned surfactant cell formers and nucleating agents added to resin component (A).
  • Aerosil R 972 is an organic
  • Hardener component (B) is used.
  • the composition comprises additives in the form of a mixture of 0.5-5% by weight of alkoxysilane, 0.5-5% by weight of hydroxyalkylene methacrylate and 0.5-5% by weight of polyethersiloxane, 0.5-5% by weight of silanized Silica, 0.1-2 wt. % Alkoxyarylsulfonic acids, in particular in the form of a mixture of 0.5-3% by weight
  • nanocrystalline silicas (aerosils).
  • alkoxysilane, hydroxyalkylene methacrylate, polyethersiloxane, silanized silica alkoxyarylsulfonic acids or mixtures thereof are the only additives of the embodiment according to the invention.
  • composition for a flame retardant synthetic resin foam contains the following components:
  • a synthetic resin selected from the group consisting of phenolic resin, melamine resin, urea resin or mixtures thereof, preferably a mixture of phenolic resin and melamine resin,
  • hardener component (B) comprising at least one reaction product of an organic nitrogen base and a polyol-phosphoric acid ester, in particular an oligomeric melamine-polyol-phosphoric acid ester,
  • filler component (C) 1-50 wt .-% filler component (C), comprising at least one inorganic filler, in particular a water of crystallization and / or
  • blowing agent component (D) comprising at least one blowing agent having a boiling point ⁇ 35 ° C at atmospheric pressure, in particular butane, isobutane, pentane, isopentane and cyclopentane and mixtures thereof.
  • the resin component (A) contains 0.5 to 10% by weight of additives which are referred to as
  • Cell formers and nucleating agents act. Further preferably contains the Hardener component (B) 0.2 to 5 wt .-% of additives that thickening and
  • Viscosity adjustment can be added.
  • the composition according to the invention for a flame retardant synthetic resin foam comprises 20-80% by weight of resin component (A), 5-40% by weight of hardener component (B), 10-50% by weight of filler component (C), 0 , 5-10% by weight of blowing agent component (D) and 0.5-10% by weight of additives, in particular 30-70% by weight of resin component (A), 5-30% by weight of hardener component (B), 10 -30% by weight
  • the composition comprises 4 parts of a mixture of resin component (A), filler component (C), fuel component (D) and further additives, wherein the resin component (A) comprises a mixture of 20-45% by weight resole resin and 2- Contains 25 wt .-% melamine resin containing the filler component 10-40 wt .-% CaSC> 4, in particular CaSÜ 4 * 2 H 2 0, a blowing agent component with 1-5 wt.%
  • Propellants in particular isobutane and / or n-pentane, additives with 0.5-3% by weight
  • B curing agent component
  • the synthetic resins contained in the resin component (A) may be used in liquid form or dissolved in another reaction component or a suitable solvent. In a preferred embodiment, in the
  • a synthetic resin selected from the group consisting of urea resin prepolymer, Melaminharzeprepolymer, Epoxydharzprepolymer or mixtures thereof used.
  • cellular foams are prepared by incorporating a propellant into
  • the invention also relates to a process for producing a flame-retardant synthetic resin foam, in particular for the production of phenolic resin foam,
  • composition used for the process according to the invention comprises, in addition to resin component (A), hardener component (B),
  • Filler component (C) and blowing agent component (D) further additives.
  • the composition used in the process corresponds to the composition according to the invention.
  • the method according to the invention relates to the production of a synthetic resin foam from the composition according to the invention.
  • the process according to the invention has the advantage that the synthetic resin foams produced by the process according to the invention show markedly improved foaming behavior, in particular do not re-foam or shrink.
  • the known compositions for polyurethane foams tend to foam strongly after being extruded from the pressure vessel, so that the volume of the synthetic resin foam continues to change over a certain period of time, especially increases.
  • Other synthetic resin foams such as phenolic, melamine and
  • Urea resin foams are often only moderately stable immediately after extrusion and tend to shrink. This is in an application as
  • the process according to the invention makes it possible to produce a fire-resistant synthetic resin foam without the extruded plastic foaming up to a great extent or shrinking due to its low stability after expansion.
  • the inventive method is characterized in that the resin component (A) is not expanded during extrusion, but prefoamed in a pressure vessel and extruded in the already foamed state from the pressure vessel.
  • the blowing agent component (D) in the resin component (A) is dissolved and prefoamed in the pressure vessel under pressure, in particular by stirring under pressure.
  • the pressure under which the prefoaming of the resin component (A) is carried out is in a range of 1-30 bar, preferably 2-30 bar, more preferably 2-20 bar, more preferably 2-10 bar, especially 4-7 bar.
  • an external pressure gas in particular an inert compressed gas such as nitrogen or argon extruded.
  • the blowing agent is used only for pre-foaming and not for extrusion as in conventional foam systems. While in conventional foam systems about 20-40% by weight of blowing agent based on the weight of the resin component is dissolved in the process according to the invention less than 20% by weight, preferably less than 15 wt .-%, more preferably less than 10 wt .-%, more preferably less than 5% by weight, in particular less than 3% by weight of
  • Propellant component (D) based on the weight of the mixture of resin component (A) and filler component (C) required.
  • Ausflowangsform of the inventive method less than 20% by weight, preferably less than 10 wt .-%, in particular less than 5 wt .-%, of the blowing agent component (D) dissolved in the resin component (A), based on the weight of the mixture of
  • Resin component (A) and filler component (C) Resin component (A) and filler component (C).
  • the volume change is synthetic resin foam, in particular the phenolic resin foam, melamine resin foam, urea resin foam or mixtures thereof after curing ⁇ 20% by volume, preferably ⁇ 10% by volume, more preferably ⁇ 7% by volume, more preferably ⁇ 5% by volume, in particular ⁇ 2% by volume, based on the initial volume of the synthetic resin foam.
  • cellular foams are prepared by incorporating a propellant into
  • Austexsform of the invention is the blowing agent component (D) in the
  • Resin component (A) dissolved and foamed in a temperature range of 20 ° C to 80 ° C, preferably in a temperature range of 15 ° C to 60 ° C, in particular in a temperature range of 20 ° C to 40 ° C at atmospheric.
  • the flow viscosity of the resin component (A) and the hardener component (B) are adjusted by admixing an aerosol (nano crystalline silicon dioxide), in particular by mixing a compound selected from the group consisting of Aerosil 90, Aerosil 130, Aerosil 150 , Aerosil 200, Aerosil 255, Aerosil 300, Aerosil 380, Aerosil OX50, Aerosil TT600, Aerosil 200F, Aerosil 380 F, Aerosil 200SP, Aerosil 300 SP or mixtures thereof, in particular Aerosil R 972 and / or Aerosil 200. Furthermore, the mixing ratio the prefoamed resin component (A) and the hardener component (B), as well as the other in the
  • Pressure vessel components such as filler component (C)
  • Propellant component (D) and additives in the extrusion of flow behavior and viscosity adjusted by adjusting the cross-section of the pipe In one embodiment, the line cross-section through which the synthetic resin or the
  • Synthetic resin foam extruded is chosen so that the resin component is metered through a 7 mm and the hardener component through a 3 mm thick hose.
  • the same partial pressures must be present in the different pressure vessels.
  • the correct mixing ratio can be achieved by adjusting the flow viscosity via the mixing of Aerosil to the resin component (A) and the hardener component (B), and by setting the appropriate line cross sections.
  • the method according to the invention comprises the following method steps:
  • Processing in the extruding a volume ratio of the curing component (B) to the mixture (AI) or (A2) of 1: 4 to 1: 5, such as 1: 4, allows.
  • volume ratio of the curing component (B) to the mixture (AI) or (A2) 1: 4 to 1: 5, such as 1: 4, is.
  • the invention also relates to a synthetic resin foam made from the
  • composition according to the invention in one embodiment, the
  • Synthetic resin foam produced from the composition according to the invention comprising resin component (A), hardener component (B) filler component (C)
  • the synthetic resin foam according to the invention comprises a resin component (A) selected from the group consisting of phenol resin, melamine resin, urea resin, alkyd resin, epoxy resin, polyester resin, polyurethane resin, polyamide resin, vinyl ester resin or mixtures thereof, preferably phenolic resin, melamine resin, urea resin or mixtures thereof, in particular a mixture of phenolic resin and melamine resin.
  • a further embodiment of the composition according to the invention relates to a 2-component can foam, in particular a mounting foam comprising at least one resin component (A) and at least one hardener component (B).
  • the resin component (A) preferably comprises a synthetic resin selected from the group consisting of
  • Melamine resins usually have a reduced shelf life, especially in the form of an aqueous solution.
  • Components can foam a reaction product of an organic nitrogen base and a polyol-phosphoric acid ester, in particular an oligomeric melamine-polyol phosphoric acid ester.
  • the reaction product of an organic nitrogen base and a polyol phosphoric acid ester is used with at least one further acid, wherein the ratio of reaction product acid 1: 4 to 4: 1, preferably 2: 1 to 4: 1 The next to the
  • Reaction product of an organic nitrogen base and a polyol used phosphoric acid esters are preferably selected from the group consisting of alkyl or arylsulfonic acids, phosphoric acids, polyphosphoric acids, acidic organic phosphates, alkylphosphinic, arylphosphinic, alkylphosphonic, arylphosphonic or mixtures thereof.
  • alkyl or arylsulfonic acids phosphoric acids
  • polyphosphoric acids polyphosphoric acids
  • acidic organic phosphates alkylphosphinic, arylphosphinic, alkylphosphonic, arylphosphonic or mixtures thereof.
  • the other organic and inorganic acids preferred within the scope of this invention may readily be used.
  • the hardener component (B) of the 2-component can foam comprises a reaction product of an organic nitrogen base and a polyol-phosphoric acid ester and at least one organic alkyl- or arylsulfonic acid further reinforced by at least one further acid selected from the group consisting of phosphoric acid , Polyphosphoric acid, acidic organic phosphates, Alkylphosphinic acid, arylphosphinic acid, alkylphosphonic acid, arylphosphonic acid or mixtures thereof.
  • the resin component (A) and hardener component (B) of the 2-component can foam are kept in stock in various pressure vessels.
  • a device with the 2-component can foam preferably comprises at least two separate pressure vessels.
  • the resin component (A) and hardener component (B) are therefore extruded from separate pressure vessels, so that resin component (A) and hardener component (B) and the other components located in the pressure vessels,
  • the 2-part can foam comprises resin component (A), resin component (B), filler component (C) and blowing agent component (D), wherein resin component (A), filler component (C) and blowing agent component (D) are preferably present in a mixture.
  • resin component (A), filler component (C) and blowing agent component (D) are preferably present in a mixture.
  • Embodiment the mixture of resin component (A), filler component (C) and blowing agent component (D) and the hardener component (B) in different
  • the known 2-component can foams, or mounting foams, with an isocyanate-bound resin component from the group of polyurethanes, show a pronounced NachSum . This is at the foaming of hollow bodies, such as in the fixation of doses of disadvantage.
  • the known mounting foams only a low thermal load in case of fire. The known mounting foams are therefore unsuitable for use as mounting foam for the fixation of cans, especially for the fixation of electrical boxes.
  • the described two-component can foam with improved post-foaming and
  • the described two-component can foam with improved NachDum- and Nachglimm for the fixation of flush boxes, especially for the fixation of surface or wall outlets selected from the group consisting of sockets, terminal boxes, screw sockets.
  • the composition of the invention itself is suitable for use as a mounting foam, in particular 2-component mounting foam with improved NachDum- and Nachglimm for foaming
  • composition of the invention is also suitable for use as a mounting foam, in the fixation of cans,
  • in particularpurpose boxes preferably selected from the group consisting of electrical boxes, telephone boxes and aerial boxes.
  • composition according to the invention is suitable for use for
  • composition of the invention can be used due to the improved Nachglimm s for foaming and the thermal insulation of hollow bodies such as cable ducts, structural cavities and suspended facade elements.
  • the composition of the invention is also suitable for use in the fixation of cans, in particular flush-mounted boxes.
  • composition of the invention is also suitable as a binder in the production of acoustic or thermal insulation panels, in particular as a binder in the production of acoustic or thermal insulation panels of mineral fibers. Unless indicated otherwise, the percentages by weight are based on the total weight of the composition according to the invention. Examples
  • Examples 1-16 describe composition according to the invention. Quantities in the tables are in grams (g)
  • compositions according to Examples 1-16 were used according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions according to their compositions
  • Components (A) to (D), and the additives used in the following process for the production of synthetic resin foams are Components (A) to (D), and the additives used in the following process for the production of synthetic resin foams.
  • Miniclave Type 1 300 mV) and heated to 50 ° C.
  • the synthetic resin foam produced in this way can be processed over a period of 1-5 minutes and, for example, smoothing and / or fitting.
  • the curing of the synthetic resin foam takes place over a period of about 10-30 min.
  • the excess material can then be removed with a spatula or suitable hand tool.
  • blowing agent component (D) At 3-5% by weight of blowing agent component (D), synthetic resin foams having a closed porosity of about 40% and a foam density of 30-200 kg / m 3 are obtained.
  • blowing agent component (D) are synthetic resin foams with a
  • the thermal conductivity of a synthetic resin foam of composition V278 is 0.0489 W / m * K at 113 kg / m 3 .
  • composition was determined.
  • a resin foam block was the size
  • FIG. 1 shows the afterglow behavior of a commercially available, unmodified
  • Phenolic resin foam compared to a synthetic resin foam of the inventive composition MG- 17.
  • Synthetic resin foam and the unmodified phenolic resin foam were prepared according to the aforementioned method example on the process steps 1-8.
  • charred phenolic resin foam is completely limited, the charring of the synthetic resin foam of the composition MG 17 to the area of flaming.

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

Abstract

La présente invention concerne une composition pour une mousse de résine synthétique difficilement inflammable comprenant un composant résineux (A), un composant durcisseur (B) et un composant de remplissage (C). Le composant résineux (A) contient une résine phénolique ou un mélange de résine phénolique et de résine de mélamine, le composant durcisseur (B) contient un produit de réaction d'une base azotée organique et d'un ester d'acide phosphorique et de polyols et le composant de remplissage (C) contient des charges inorganiques finement broyées. La présente invention concerne en outre des procédés de fabrication d'une mousse de résine synthétique difficilement inflammable selon l'une des revendications 1 à 6, en particulier, de fabrication de mousse de résine phénolique, de mousse de résine de mélamine, de mousse de résine d'urée ou de leurs mélanges, comprenant les étapes de procédé suivantes : (i) dissolution du composant moussant (D) dans le mélange constitué du composant résineux (A) et du composant de remplissage (C), (ii) pré-moussage du mélange constitué du composant résineux (A) et du composant de remplissage (C) avec le composant moussant (D), et (iii) extrusion et mélange du mélange constitué du composant résineux (A), du composant de remplissage (C) et du composant moussant (D) avec le composant durcisseur (B).
PCT/EP2013/058076 2012-04-18 2013-04-18 Composition pour une mousse de résine synthétique difficilement inflammable et son procédé de fabrication WO2013156562A2 (fr)

Applications Claiming Priority (2)

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DE102012206366.8A DE102012206366B4 (de) 2012-04-18 2012-04-18 Zusammensetzung für einen schwer entflammbaren Kunstharzschaum, sowie Verfahren zu dessen Herstellung
DE102012206366.8 2012-04-18

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2717775A1 (de) 1976-05-24 1977-12-01 Armstrong Cork Co Phenolharz-schaumstoff
DE2825295B1 (de) 1978-06-09 1979-11-08 Ruehl Erich Chem Fab Werkstoff und Verfahren zu seiner Herstellung
DE3407512C1 (de) 1984-03-01 1985-04-18 Erich 6382 Friedrichsdorf Rühl Verbessertes Fuellstoffsystem fuer einen nicht brennbaren Hartschaum und seine Verwendung als Baustoff
US4681902A (en) 1985-11-16 1987-07-21 Bp Chemicals Limited Flame retardant phenolic foams
DE3800584A1 (de) 1988-01-12 1989-07-20 Ruehl Erich Nicht brennbarer, fuellstoff enthaltender hartschaum auf phenol-furanharzbasis
WO1999005200A1 (fr) 1997-07-25 1999-02-04 Nycomed Imaging As Procede servant a preparer des phosphates de polyether
DE10112155A1 (de) 2001-03-14 2002-09-19 Budenheim Rud A Oetker Chemie Derivat von Phosphorsäureestersatz oder-addukt oder Gemischen hiervon, Verfahren zu deren Herstellung und deren Verwendung

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4227536C1 (de) 1992-08-20 1994-01-05 Erich Ruehl Ag Chem Fab & Co H Nicht brennbarer, Füllstoff enthaltender Hartschaum auf Phenol-Furanharzbasis
DE10150737A1 (de) 2001-10-15 2003-04-30 Hilti Ag Mehrkomponenten-Ortschaumsystem und dessen Verwendung
AT412279B (de) 2003-04-14 2004-12-27 Intumex Gmbh Im brandfall ein zweites mal expandierende weichschaumstoffe auf basis von styrol-butadien, polyvinylalkohol oder neopren
WO2004099292A1 (fr) 2003-05-09 2004-11-18 Prometheus Developments Limited Procede de production d'un materiau polymere
DE102007009127A1 (de) 2006-03-09 2007-09-13 Basf Ag Faserverstärkter Schaumstoff auf Basis von Melaminharzen

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2717775A1 (de) 1976-05-24 1977-12-01 Armstrong Cork Co Phenolharz-schaumstoff
DE2825295B1 (de) 1978-06-09 1979-11-08 Ruehl Erich Chem Fab Werkstoff und Verfahren zu seiner Herstellung
DE3407512C1 (de) 1984-03-01 1985-04-18 Erich 6382 Friedrichsdorf Rühl Verbessertes Fuellstoffsystem fuer einen nicht brennbaren Hartschaum und seine Verwendung als Baustoff
US4681902A (en) 1985-11-16 1987-07-21 Bp Chemicals Limited Flame retardant phenolic foams
DE3800584A1 (de) 1988-01-12 1989-07-20 Ruehl Erich Nicht brennbarer, fuellstoff enthaltender hartschaum auf phenol-furanharzbasis
WO1999005200A1 (fr) 1997-07-25 1999-02-04 Nycomed Imaging As Procede servant a preparer des phosphates de polyether
DE10112155A1 (de) 2001-03-14 2002-09-19 Budenheim Rud A Oetker Chemie Derivat von Phosphorsäureestersatz oder-addukt oder Gemischen hiervon, Verfahren zu deren Herstellung und deren Verwendung

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DE102012206366B4 (de) 2022-05-19
WO2013156562A3 (fr) 2014-03-20

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