WO2011113795A2 - Mousse composite ignifugée - Google Patents

Mousse composite ignifugée Download PDF

Info

Publication number
WO2011113795A2
WO2011113795A2 PCT/EP2011/053808 EP2011053808W WO2011113795A2 WO 2011113795 A2 WO2011113795 A2 WO 2011113795A2 EP 2011053808 W EP2011053808 W EP 2011053808W WO 2011113795 A2 WO2011113795 A2 WO 2011113795A2
Authority
WO
WIPO (PCT)
Prior art keywords
component
optionally
composite foam
weight
alkyl
Prior art date
Application number
PCT/EP2011/053808
Other languages
German (de)
English (en)
Other versions
WO2011113795A3 (fr
Inventor
Maxim Peretolchin
Tobias Heinz Steinke
Matthias Pfeiffer
Sabine Fuchs
Ingo Bellin
Klaus Hahn
Günter Scherr
Karl-Heinz Schmitz
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
Publication of WO2011113795A2 publication Critical patent/WO2011113795A2/fr
Publication of WO2011113795A3 publication Critical patent/WO2011113795A3/fr

Links

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
    • C08J9/0014—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
    • C08J9/0066—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
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products
    • C08J9/236—Forming foamed products using binding agents
    • 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
    • C08J9/33—Agglomerating foam fragments, e.g. waste foam
    • 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
    • C08J9/35—Composite foams, i.e. continuous macromolecular foams containing discontinuous cellular particles or fragments
    • 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
    • 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
    • C08J2425/00—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

Definitions

  • the invention relates to a flame-retardant composite foam comprising a styrene polymer and an aminoplast, a composition and a process for producing the composite foam and its use as insulating material.
  • EP-A 0 806 451 flame-retardant polystyrene foams which contain - in the polystyrene foam - a combination of phosphorus compounds and sulfur as a flame retardant. It is proposed to optionally encapsulate the sulfur, wherein as a possible capsule material and melamine-formaldehyde resins are mentioned.
  • Composite foams which contain a styrene polymer, such as polystyrene, and an aminoplast, such as melamine-formaldehyde resins or urea-formaldehyde resins, are known, for example, from DE-A 1 479 972, DE-A 23 52 969 and WO 2008/105595. In the latter document is described to add a siliziumoxid ambiences flame retardant to the foam.
  • the invention therefore relates to a composite foam containing A) foamed particles containing
  • A1 from 25 to 95% by weight of styrene polymer (e), A2) optionally a blowing agent,
  • A3) optionally one or more additives,
  • the invention further provides a composition for producing the composite foam according to the invention, comprising a) an expandable, optionally prefoamed granules comprising a1) from 25 to 65% by weight of styrene polymer (e), a2) a blowing agent, optionally one or more additives, b ) a solution or dispersion of a curable aminoplast component containing b1) 1 to 65 wt .-% curable, optionally modified aminoplast resin, b2) 0.1 to 20 wt .-% of one or more flame-retardant organic phosphorus compounds having a phosphorus content of 5 to 80 wt .-% (based on the respective phosphorus compound b) optionally one or more flame-retardant synergists for component b2), b4) optionally a blowing agent, b5) optionally one or more additives, b6) one or more dispersants, b7) one or more hardeners, wherein the weight percentages -
  • the invention likewise provides a process for producing the foam according to the invention, comprising the steps of i) providing a solution or dispersion of the optionally modified aminoplast resin component b) by homogeneously mixing components b1), b2), b6), b7) and optionally b3) to b5), ii) providing the expandable particles a), iii) optionally pre-foaming the particles a), iv) mixing the components a) and b), so that a mixture containing 25 to 95 wt .-% of the component a1) , 1 to 65 wt .-% of component b1) and 0.1 to 20 wt .-% of component b2), based on the sum of components a1), b1) and b2), gives, v) curing of component b1 ), optionally foaming the component b1) and vii) optionally foaming the component a), wherein the steps v) and / or vi) and / or vii
  • the invention further relates to the use of the composite foam according to the invention as insulating material, in particular for buildings.
  • the composite foam according to the invention generally has a density in the range from 5 to 120 kg / m 3 , preferably 8 to 60 kg / m 3 , particularly preferably 10 to 35 kg / m 3 .
  • the particle foam component A) contains at least one styrene polymer as component A1).
  • component A1) consists of one or more, preferably a styrene polymer.
  • styrene polymer comprises polymers based on styrene, ⁇ -methylstyrene or mixtures of styrene and ⁇ -methylstyrene; This applies analogously to the styrene content in SAN, AMSAN, ABS, ASA, MBS and MABS (see below).
  • Inventive styrene polymers are based on at least 50 parts by weight of styrene and / or alpha-methylstyrene monomers.
  • styrene polymers to glassy polystyrene (GPPS), toughened polystyrene (HIPS), anionically polymerized polystyrene or toughened polystyrene (A-IPS), styrene-alpha-methstyrene copolymers, acrylonitrile-butadiene-styrene polymers (ABS), styrene-acrylonitrile copolymers (SAN), acrylonitrile-alpha-methylstyrene copolymers (AMSAN), acrylonitrile-styrene-acrylic ester (ASA), methyl acrylate-butadiene-styrene (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) polymers or mixtures thereof or with polyphenylene ether (PPE) used.
  • GPPS glassy polystyrene
  • HIPS toughened polystyrene
  • thermoplastic polymers such as polyamides (PA), polyolefins, such as polypropylene (PP) or polyethylene (PE), polyacrylates, such as polymethyl methacrylate (PMMA), polycarbonate ( PC), polyesters such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), polyether sulfones (PES), polyether ketones, polyether sulfides (PES) or mixtures thereof in proportions of not more than 30 parts by weight, preferably in the range of 1 to 10 wt.
  • PA polyamides
  • PE polyolefins
  • PMMA polymethyl methacrylate
  • PC polycarbonate
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PES polyether sulfones
  • PES polyether ketones
  • mixtures in the mentioned quantitative ranges are also included, for example hydrophobically modified or functionalized polymers or oligomers, rubbers such as polyacrylates or polydienes, for example styrene-butadiene block copolymers or biodegradable aliphatic or aliphatic / aromatic copolyesters.
  • Suitable compatibilizers are, for example, maleic anhydride-modified styrene copolymers, epoxy-group-containing polymers or organosilanes.
  • foams according to the invention which contain, as component A1) polystyrene and preferably consist thereof, in particular the types of commercially available Neopor ®, polystyrene ® and Peripor ® (all from BASF SE, Ludwigshafen, Germany).
  • Expandable styrene polymers preferably have a molecular weight M w in the range from 120,000 to 400,000 g / mol, more preferably in the range from 180,000 to 300,000 g / mol, measured by gel permeation chromatography according to DIN 55672-1 with refractometric detection (RI) in relation to polystyrene standards, on. Due to the reduction in molecular weight by shear and / or temperature, the molecular weight of the expandable polystyrene is usually about 10,000 g / mol below the molecular weight of the polystyrene used.
  • the polymerization is carried out, for example, by bulk polymerization, solution polymerization or by emulsion, suspension or dispersion polymerization.
  • the suspension polymerization is preferred.
  • In the suspension polymerization is preferably used as the monomer styrene alone. However, up to 20% of its weight may be replaced by other ethylenically unsaturated monomers such as alkylstyrenes, divinylbenzene, acrylonitrile, 1,1-diphenyl ether or alpha-methylstyrene.
  • the monomers from which the preferred polymers are obtainable are preferred.
  • the production of the particle foam component A) according to the invention is generally carried out from a polymer melt.
  • the polymer melt can also polymer recyclates of said thermoplastic see polymers, in particular styrene polymers and expandable styrene polymers (EPS) are admixed in amounts that do not significantly deteriorate their properties, usually in amounts of up to 50 parts by weight, in particular in amounts of 1 to 20 parts by weight, based on 100 parts by weight of the styrene polymer component A).
  • EPS expandable styrene polymers
  • conventional additives A3) such as nucleating agents, fillers, plasticizers, soluble and insoluble inorganic and / or organic dyes and pigments, for example IR absorbers such as carbon black, flake graphite or aluminum powder, may be jointly or spatially separated from the polymer melt, for example via mixers or Side extruders are added.
  • the dyes and pigments are added in amounts ranging from 0.01 to 30, preferably in the range of 1 to 5 parts by weight, based on 100 parts by weight of component a1).
  • a dispersing aid for example organosilanes, epoxy-group-containing polymers or maleic anhydride-grafted styrene polymers.
  • Preferred plasticizers are mineral oils, phthalates, which can be used in amounts of 0.05 to 10 parts by weight, based on 100 parts by weight of component a).
  • the styrene polymer particles themselves may also have one or more, preferably halogen-free, flame-retardant and / or synergistic compounds - preferably those in components B2) and B3) mentioned phosphorus compounds and optionally their synergists -. If present, the proportion of such additional flame retardant compounds is usually 0.5 to 5 parts by weight (based on 100 parts by weight of a1)).
  • the additives of component A3) are located in the particle foam A) and are thus clearly distinguishable from the additives of component B) present in the aminoplast resin.
  • EPS foams used according to the invention as component A
  • EPS foams can be processed by adding a blowing agent into the polymer melt, extrusion and granulation under pressure to expandable granules (EPS) and optionally by subsequent pre-foaming of the granules to the EPS particle foam.
  • the blowing agent-containing polymer melt generally contains one or more blowing agents in a homogeneous distribution in a proportion of 2 to 10 parts by weight, preferably 3 to 7 parts by weight, based on 100 parts by weight of the polymer melt.
  • Suitable blowing agents are the physical blowing agents commonly used in EPS, such as aliphatic hydrocarbons having 2 to 7 carbon atoms, alcohols, ketones, ethers or halogenated hydrocarbons. Preference is given to isobutane, n-butane, Iso-pentane, n-pentane or isomer mixtures used, for example, mixtures of n- and iso-pentane.
  • finely divided internal water droplets can be introduced into the polymer matrix. This can be done for example by the addition of water in the molten polymer matrix. The addition of the water can be done locally before, with or after the propellant dosage. A homogeneous distribution of the water can be achieved by means of dynamic or static mixers. As a rule, from 0 to 2, preferably from 0.05 to 1.5, parts by weight of water, based on 100 parts by weight of component A), are sufficient.
  • Expandable styrene polymers with at least 90% of the internal water in the form of inner water droplets with a diameter in the range of 0.5 to 15 ⁇ form during foaming foams with sufficient cell count and homogeneous foam structure.
  • the amount of blowing agent and water added is chosen such that the expandable styrene polymers (EPS) have an expansion capacity a, defined as bulk density, before foaming / bulk density after being put on at most 125, preferably 15 to 100.
  • EPS expandable styrene polymers
  • the expandable styrene polymer pellets (EPS) used according to the invention as component A) generally have a bulk density of at most 700 g / l, preferably in the range from 590 to 660 g / l. When using fillers, depending on the type and amount of the filler, bulk densities in the range of 590 to 1200 g / l may occur.
  • the composite foam of the invention contains in component B) at least one cured, optionally modified and optionally foamed aminoplast resin, ie a polycondensation product obtained by reacting a carboxyl compound with a component containing an amino, imino or amide group.
  • component B1 are condensation products of formaldehyde with melamine, urea, urethanes, cyano or dicyanamide, aromatic amines and / or sulfonamides.
  • melamine-formaldehyde (MF) condensates particularly preferred are melamine-formaldehyde (MF) condensates, melamine-urea-formaldehyde (MHF) condensates and urea-formaldehyde (HF) condensates, particularly preferred are MF condensates.
  • MF condensates may be partially or completely etherified with alcohols, preferably C 1 -C 4 -alcohols, in particular methanol or ethanol.
  • the optionally modified aminoplast resins B1) may contain, for example, acetaldehyde, trimethylolacetaldehyde, acrolein, furfurol, glyoxal, phthalaldehyde and / or terephthalaldehyde.
  • the curable aminoplast resin is usually used as a solution or dispersion which is cured during the production of the composite foam according to the invention.
  • the aminoplast resin is usually present at 20 to 70 wt .-%, in particular at 30 to 60 wt .-%, before.
  • auxiliaries and additives known to the person skilled in the art, for example urea, caprolactam, phenyldiglycol, butanediol and saccarose.
  • the aminoplast resins B1) may be unmodified, but they may also be modified. "Modified” in the sense of the invention means that 0 to 30 mol% of the amine component (for example of the melamine), preferably up to 20 mol%, particularly preferably up to 10 mol%, particularly preferably up to 5 mol%, be replaced by other known Duroplasttruckner, preferably phenol and phenol derivatives.
  • the aminoplast resin component B1) consists of unmodified aminoplast resin (s).
  • the composite foam according to the invention contains as component B2) preferably at least one compound of the formula (I) having a phosphorus content of from 5 to 80% by weight, based on the phosphorus compound,
  • R 1 is C Ci 6 alkyl, d-do-hydroxyalkyl, C 2 -C 6 alkenyl, C Ci 6 alkoxy, C 2 -C 6 - alkenoxy, C 3 -C 0 cycloalkyl, C 3 -C 0 -Cycloalkoxy, C 6 -Cio-Aryl, C 6 -Cio-Aryloxy, C 6 -Cio-Aryl-Ci-Ci6-Alkyl, C 6 -Cio-Aryl-Ci-Ci 6 -Alkoxy, SR 9 , COR 10 , COOR 11 , CONR 12 R 13 ;
  • R 2 is C Ci 6 alkyl, C 0 Ci hydroxyalkyl, C 2 -C 6 alkenyl, C Ci 6 alkoxy, C 2 -C 6 - alkenoxy, C 3 -C 0 cycloalkyl, C 3 -C 0 cycloalkoxy, C 6 -C 0 aryl, C 6 -C 0 aryl-Ci-Cie alkyl, C 6 -Cio-aryl-Ci-Ci 6 alkoxy, SR 9, COR 10, COOR 11, CONR 12 R 13 ;
  • R 3 is H, SH, SR 4 , OH, OR 5 or a group
  • X 1 , X 2 , X 3 are identical or different and independently of one another O or S; Y 1 , Y 2 are the same or different O or S;
  • R 4 , R 5 , R 9 , R 10 , R 11 , R 12 , R 13 are identical or different C 1 -C 2 -alkyl, C 3 -C 8 -
  • Cycloalkyl which is unsubstituted or substituted by one or more -C 4 alkyl groups, C 2 -C 2 -alkenyl, C 2 -C 2 alkynyl, C 6 -C 0 aryl or C 6 -C 0 aryl-Ci- C 4 alkyl;
  • R 6 , R 7 , R 8 are identical or different and independently of one another are C 1 -C 6 -alkyl
  • R 1 is preferably CRCI 6 alkyl, Ci-Ci 0 hydroxyalkyl, C 2 -C 6 alkenyl, d-
  • R 2 is preferably CRCI 6 alkyl, Ci-Ci 0 hydroxyalkyl, CRCI 6 alkenyl, d-
  • R 3 is preferably H, SH, SR 4 , OH, OR 5 or a group:
  • X 1 , X 2 and X 3 are preferably identical or different independently of one another O or S.
  • Y 1 , Y 2 are preferably the same or different O or S.
  • R 4, R 5 are preferably the same or different Ci-Ci 2 -alkyl, C 3 -C 8 - cycloalkyl, unsubstituted or substituted by one or more CrC 4 -
  • alkyl C 2 -C 2 -alkenyl, C 2 -C 2 alkynyl, C 6 -C 0 - aryl or C 6 -C 0 aryl-Ci-C 4 alkyl.
  • R 6, R 7, R 8 are preferably identical or different independently of each other d-Cie-alkyl, Ci C 6 alkenyl, C Ci 6 alkoxy, Ci C 6 -alkenoxy, C3-C1 0 -
  • n is preferably 1 if Y 1 or Y 2 is O, and 1 or 2 if Y 2 is S and m is preferably an integer from 0 to 10.
  • s, t, u are preferably 1.
  • R 1 is particularly preferably C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, cyclohexyl, phenyl,
  • R 2 is particularly preferably -C 8 alkyl, -C 8 alkoxy, cyclohexyl, phenyl,
  • R 3 is more preferably H, SH, SR 4 , OH, OR 5 or a group
  • X 1 and X 3 are more preferably the same or different O or S.
  • Y 1 is more preferably O or S.
  • R 4 , R 5 are particularly preferably identical or different C 1 -C 8 -alkyl, cyclohexyl,
  • R 7 , R 8 are more preferably identical or different and are C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, cyclohexyl, phenyl, phenoxy, benzyl and benzyloxy.
  • n is more preferably 1 if Y 1 is O and 1 or 2 if Y 1 is S. s and t are particularly preferred 1.
  • R 1 is particularly preferably phenyl, phenyloxy.
  • R 2 is particularly preferably phenyl.
  • R is particularly preferably H, SH, SR, OH, OR or a group
  • X 1 and X 3 are particularly preferably the same or different O or S.
  • Y 1 is particularly preferably O or S.
  • R 4 , R 5 are particularly preferably identical or different cyclohexyl, phenyl or benzyl.
  • R 7 , R 8 are particularly preferably identical or different phenyl, phenoxy.
  • n is preferably 1 if Y 1 is O and 1 or 2 if Y 1 is S. s and t are particularly preferred 1.
  • the compounds of formula (I) are partially available commercially, e.g. FSM1 from ABCR GmbH & Co KG, Düsseldorf, Germany, FSM5 as HCA from Sanko, and FSM6 as Cyagard RF-1241 from Cytech.
  • the flame retardants FMS 2, 3 and 4 can be prepared, for example, according to the following references:
  • FSM2 JIG Cadogan; JB Husband; H. McNab; J. Chem. Soc. Perkin Trans. I .; 1983; 1489 to 1495.
  • FSM3 MG Zimin, NG Zabirov; V. Smirnov; Zhournal Obschei Khimii; 1980; 50; 1 ; 24 to 30.
  • component B2 is expandable graphite. Due to its layered lattice structure, graphite is able to form special forms of intercalation compounds. In these so-called interstitial compounds, foreign atoms or molecules have been taken up in some cases in stoichiometric ratios in the spaces between the carbon atoms. These graphite compounds, for example with sulfuric acid as a foreign molecule, which are also produced on an industrial scale, are referred to as expandable graphite.
  • the density of this expandable graphite is in the range of 1, 5 to 2.1 g / cm 3 , the particle size at 100 to 1000 ⁇ . Under the effect of heat, the layers are forced apart like an accordion by thermolysis, the graphite flakes expand.
  • the expansion can start at around 150 ° C and take place almost instantaneously. With free expansion, the final volume can reach several hundred times the initial volume.
  • the expanded expanded graphite forms an intumescent layer on the foam surface and thus slows down the fire evaluation.
  • Expandable graphite is commercially available, for example from Graphit Kropfmühl AG, Hauzenberg, Germany.
  • Expandable graphite as component B2) is preferably used alone.
  • the component B2) contains only one or more of said phosphorus compounds.
  • the composite foam according to the invention optionally contains one or more flame retardant synergists. Synergists from the group of elemental sulfur, thermal radical formers such as dicumyl peroxide, di-tert-butyl peroxide and biscumyl (2,3-diphenyl-2,3-dimethyl-butane), metal oxides, metal hydroxides such as Sb 2 0 3 are preferred and Sn compounds, and nitroxyl radical-containing or releasing compounds.
  • Expanded graphite is preferably used without synergist B3).
  • synergist B3 is elemental sulfur, in particular in combination with one or more of the indicated phosphorus compounds, in particular those of the formula (I).
  • the elemental sulfur is preferably distributed substantially homogeneously in the polymer foam, which can be achieved, for example, by admixture during extrusion or by static or dynamic mixers (eg kneaders).
  • the elemental sulfur can also be used in the form of starting compounds which are decomposed under the process conditions to elemental sulfur.
  • the weight ratio of component B2) (flame retardant compound (s)) to component B3) (synergist (s)) is generally 1: 0.1-10, preferably 1: 0.2-7, particularly preferably 1: 0.3 - 5 and in particular 1: 0.3 - 3.
  • halogen-reduced polymer compositions can be obtained by the use of component B2) according to the invention and the addition of lesser amounts of halogen-containing, in particular brominated flame retardants, such as hexabromocyclododecane (HBCD) or brominated styrene homo- or styrene copolymers / oligomers (eg styrene).
  • HBCD hexabromocyclododecane
  • Butadiene copolymers as described in WO-A 2007/058736
  • Suitable additives B5) used are, for example, the fillers, dyes and pigments mentioned above (component A3)), which are optionally added to component A) and / or component B).
  • additives B5 are inorganic nanoparticles, as described, for example, in WO 2007/048731.
  • inorganic nanoparticles aluminum oxide, silicon oxide, titanium dioxide, tin oxide, yttrium oxide, cerium oxide, zinc oxide and / or silicon carbide are advantageously used.
  • alumina, silica and / or silicon carbide are used.
  • These particles advantageously have an average particle diameter of from 2 to 500 nm, preferably from 3 to 150 nm, particularly preferably from 5 to 60 nm, in particular from 10 to 40 nm.
  • Further preferred additives B5) are urea, caprolactam, phenyldiglycol, butanediol and / or saccharose, furthermore customary additives such as wetting agents and catalysts.
  • the aminoplast resin b1) is typically used in admixture with one or more of the components b6), b7) and optionally b4) and b5):
  • Component b4) - Propellant In principle, both physical and chemical blowing agents can be used in the process according to the invention (Encyclopedia of Polymer Science and Technology, Vol. I, 3rd ed., Chapter Additives, pages 203 to 218, 2003).
  • blowing agents are "physical” or “chemical” blowing agents.
  • physical propellants is meant here volatile liquids or compressed gases which obtain their property as propellants by physical treatment (eg temperature, pressure).
  • Chemical propellants are understood here to mean those propellants which have their property as propellants by chemical means Reaction or chemical decomposition with gas release obtained.
  • Suitable "physical" blowing agents are, for example, hydrocarbons, such as pentane, hexane, halogenated, in particular chlorinated and / or fluorinated hydrocarbons, for example methylene chloride, chloroform, trichloroethane, chlorofluorocarbons, hydrochlorofluorocarbons (HCFCs), alcohols, for example methanol, ethanol, n or isopropanol, ethers, ketones and esters, for example methyl formate, ethyl formate, methyl acetate or ethyl acetate in liquid form, or air, nitrogen and carbon dioxide as gases
  • Suitable "chemical" blowing agents are, for example, isocyanates in a mixture with water, where effective Propellant carbon dioxide is released. Further, carbonates and bicarbonates are suitable in admixture with acids which also produce carbon dioxide. Also suitable are azo compounds, e.g. Azodicarbonamide.
  • the propellant consists of one or more compounds.
  • anionic, cationic and nonionic surfactants and mixtures thereof can be used.
  • anionic surfactants are diphenylene oxide sulfonates, alkane and alkylbenzenesulfonates, alkylnaphthalenesulfonates, olefinsulfonates, alkyl ether sulfonates, fatty alcohol sulfates, ether sulfates, alpha-sulfofatty acid esters, acylaminoalkanesulfonates, acylisothionates, alkylethercarboxylates, N-acylsarcosinates, alkyl and alkyl ether phosphates.
  • nonionic surfactants for example, alkylphenol polyglycol ethers, fatty alcohol polyglycol ethers, fatty acid polyglycol ethers, fatty acid alkanolamides, ethylene oxide / propylene oxide block copolymers, amine oxides, glycerol fatty acid esters, sorbitan esters and alkylpolyglycosides can be used.
  • cationic emulsifiers e.g. Alkyltriammoniumsalze, Alkylbenzyldimethylammoniumsalze and Alkylpyridiniumsalze be used.
  • Suitable hardeners are in particular acidic compounds, such as inorganic Br ⁇ nsted acids, for example sulfuric acid or phosphoric acid, organic Br ⁇ nsted acids, such as acetic acid or formic acid, Lewis acids and also so-called latent acids, ie salts of said acids with NH 3 , amines, Aminoalcohols etc ..
  • the production of the composite foams according to the invention can be carried out by various methods.
  • the aminoplast component b) can optionally be foamed before or after mixing with the component a), wherein the foaming can be carried out mechanically, by admixing air or other gases or by blowing agent.
  • the expandable granules of the styrene polymer a) is optionally prefoamed to a desired density prior to mixing with component b) in a conventional apparatus suitable for the production of EPS.
  • Typical bulk densities of the prefoamed granules are in the range of 8-50 kg / m 3 .
  • the mixing of the components a) and b) is carried out by a coating of the optionally prefoamed or foamed Particle foam component a) with the optionally foamed aminoplast resin component b).
  • the interstices between the particle foam particles a) are filled by the aminoplast resin component b).
  • the mixture of components a) and b) is optionally further foamed, for example mechanically, by admixing air or other gases or the use of blowing agents, and then the resin component b) cured at room temperature or application of heat.
  • the heat can be entered for example by microwave or IR irradiation or use of a furnace.
  • the mixture is compressed in a preferred embodiment.
  • the particle foam component a) and / or the resin component b) are further foamed or expanded. In this way, various embodiments of the composite foam can be produced.
  • composite foam sheets are produced in suitable forms.
  • the composite foam is used as a mass for filling cavities in walls or building materials, in particular building blocks, such as hollow bricks or Porotonsteinen.
  • the optionally prefoamed granules of the particle foam are preferably coated with a mixture of the components and the granules are bonded by the action of heat. An additional bonding then takes place during welding of the granules, similar to the post-foaming in the conventional EPS production.
  • the welding is carried out in conventional block machines for the production of EPS blocks. The heat is supplied by steam or heated air.
  • the composite foam according to the invention is particularly suitable as insulating material for the construction industry, i. in the construction, renovation and repair of buildings, for example for thermal insulation and the production of composite materials.
  • DOPO 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
  • Pentane commercial mixture of n- and iso-pentane (s-pentane)
  • EPS Neopor ® P 5200 (BASF SE)
  • a spray-dried MF precondensate (molar ratio 1: 1, 7) were dissolved in 25 parts by weight of water.
  • the solution was treated with 15% formic acid, 2% of a sodium-Ci 2 / Ci 5 -alkylsulfonate, 5% pentane (based on the MF precondensate) and 1% DOPO / S (in a ratio by weight of 2.5: 1 , 5), based on the solid amount of EPS and MF precondensate, added.
  • the obtained mixture was thoroughly mixed and then treated with 66% by weight of prefoamed polystyrene particles having a diameter of 4-5 mm and a density of 17 g / l.
  • the mixture was foamed in a polypropylene foam mold by irradiation with microwaves at 2.54 GHz.
  • the foam was dried for 4 h at 100 ° C.
  • the composite foam thus produced had a density of 35 g / l, a thermal conductivity of 33 mW / m * K and meets the requirements of fire class B2 according to DIN 4102.
  • a spray-dried MF precondensate (molar ratio 1: 1, 7) were dissolved in 25 parts by weight of water.
  • the solution was mixed with 15% formic acid, 2% of a sodium Ci 2 / Ci 5 alkyl sulfonate, 5% pentane (in each case based on the solids content of the MF precondensate) and 1% DOPO / S (in a ratio 2.5: 1 , 5), based on the amount of solids of EPS and MF precondensate, added.
  • the obtained mixture was thoroughly mixed and then treated with 66% by weight of prefoamed polystyrene particles having a diameter of 5 mm and a density of 17 g / l.
  • the mixture in foam form was added to the facsimile Tor 40% compressed and heated to 100 ° C for 3 h.
  • the foam was removed from the foam mold and dried for an additional 4 hours at 100 ° C.
  • the composite foam produced in this way had a density of 50 g / l, a thermal conductivity of 32.7 mW / m * K (measured in accordance with DIN 13163) and met the requirements for fire class B2 in accordance with DIN 4102.
  • a spray-dried MF precondensate (molar ratio 1: 1, 7) were dissolved in 25 parts by weight of water.
  • the solution was mixed with 15% formic acid, 2% of a sodium Ci 2 / Ci 5 alkyl sulfonate, 5% pentane (in each case based on the solids content of the MF precondensate) and 1% DOPO / S (in a ratio 2.5: 1 , 5), based on the amount of solids of EPS and MF precondensate, added.
  • the obtained mixture was thoroughly mixed and then treated with 66% by weight of prefoamed polystyrene particles having a diameter of 5 mm and a density of 17 g / l.
  • the mixture was then heated to 80 ° C in a wooden frame construction for 45 min.
  • the foam was removed from the foam mold and dried for a further 48 h at 25 ° C.
  • the composite foam thus produced had a density of 50 g / l, a thermal conductivity of 32.4 mW / m * K and meets the requirements of fire class B2 according to DIN 4102.
  • a spray-dried MF precondensate (molar ratio 1: 1, 7) were dissolved in 25 parts by weight of water.
  • the solution was with 15% formic acid, 2% of a sodium Ci 2 / Ci 5 alkyl sulfonate, 5% pentane (each based on the solids content of the MF precondensate) and 2% expandable graphite ES 350 F5 Fa.
  • Graphit Kropfmühl AG based on the amount of solids of EPS and MF precondensate, added.
  • a Porotonstein (type POROTON T-8 without filling, Fa. Wienerberger AG, Vienna, Austria) was placed on a plate and filled with the mixture described in Example 3 so that all cavities (total volume about 13.2 I) were filled.
  • the stone was covered with a second plate, placed in an oven at 80 ° C for 45 minutes and then dried for two days at room temperature.
  • the finished stone had a firm and stable filling, which sits firmly in the cavities and could only be scraped out by using strong forces.
  • the total amount of filling after 34 days was 615 g (corresponding to an unfavorable filling density of 47 kg / m 3 ).
  • the filling showed excellent flame resistance, so that a butane-powered gas burner with an approximate flame temperature of 1200 ° C caused little damage to the filling (depression of less than 2 cm).

Landscapes

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

Abstract

L'invention concerne une mousse composite contenant A) des particules moussées contenant A1) de 25 à 95 % en poids de polymère(s) de styrène, A2) éventuellement un agent d'expansion, A3) éventuellement un ou plusieurs additifs, B) un composant aminoplaste contenant B1) de 1 à 65 % en poids de résine aminoplaste durcie, éventuellement modifiée et éventuellement moussée, B2) de 0,1 à 20 % en poids d'un ou plusieurs composés du phosphore organique retardateurs de flamme, ayant une teneur en phosphore de 5 à 80 % en poids (par rapport au composé concerné), et/ou du graphite expansé, B3) éventuellement un ou plusieurs synergistes retardateurs de flamme pour les composants B2, B4) éventuellement un agent d'expansion, B5) éventuellement un ou plusieurs additifs, les pourcentages en poids - sauf indication contraire - se rapportant à la somme des composants A1), B1) et B2). Cette mousse composite convient en particulier comme matériau isolant.
PCT/EP2011/053808 2010-03-17 2011-03-14 Mousse composite ignifugée WO2011113795A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP10156713 2010-03-17
EP10156713.9 2010-03-17

Publications (2)

Publication Number Publication Date
WO2011113795A2 true WO2011113795A2 (fr) 2011-09-22
WO2011113795A3 WO2011113795A3 (fr) 2011-12-01

Family

ID=44509851

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2011/053808 WO2011113795A2 (fr) 2010-03-17 2011-03-14 Mousse composite ignifugée

Country Status (1)

Country Link
WO (1) WO2011113795A2 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2735584A1 (fr) * 2012-11-26 2014-05-28 Basf Se Mousse en résine en mélamine déformable à chaud avec matériau de remplissage à particules
EP2743296A1 (fr) * 2012-12-11 2014-06-18 STO SE & Co. KGaA Procédé de fabrication d'un élément d'isolation ignifuge, élément d'isolation ainsi que l'utilisation d'un élément d'isolation
EP2873779A1 (fr) * 2013-11-13 2015-05-20 STO SE & Co. KGaA Procédé de fabrication d'un corps moulé à plusieurs couches et corps moulé à plusieurs couches destiné à l'isolation thermique de bâtiments
EP3530689A1 (fr) 2018-02-21 2019-08-28 Basf Se Pièce moulée et mélange et son procédé de fabrication
WO2021032738A1 (fr) 2019-08-21 2021-02-25 Basf Se Particules de mousse à écoulement libre et moulages en mousse de particules ignifuges

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1479972A1 (de) 1962-01-26 1969-03-27 Basf Ag Verfahren zur Herstellung kombinierter Schaumstoffe
DE2352969A1 (de) 1973-10-23 1975-04-30 Basf Ag Verfahren zur herstellung von harten schaumstoffen mit hoher feuerwiderstandsdauer
EP0806451A1 (fr) 1996-05-06 1997-11-12 Albemarle Corporation Compositions de styrènes-polymères retardatrices de flamme
DE19910257A1 (de) 1999-03-08 2000-09-21 Schwenk Daemmtechnik Gmbh & Co Flammhemmend ausgerüstete Schaumstoffe auf Basis von Styrolpolymerisaten
GB2362586A (en) 2000-05-24 2001-11-28 Prometheus Developments Ltd Fire stable expanded polystyrene foam materials
US20040115455A1 (en) 2001-02-14 2004-06-17 Quist Per Ingmar Polymeric composite foam
WO2007048731A1 (fr) 2005-10-27 2007-05-03 Basf Se Film de resines aminoplastiques comprenant un papier impregne d’un melange de resines aminoplastiques comprenant des nanoparticules inorganiques
WO2007058736A1 (fr) 2005-11-12 2007-05-24 Dow Global Technologies Inc. Copolymeres de butadiene et de vinyle aromatique bromes, melanges de tels copolymeres avec un polymere de vinyle aromatique et mousses polymeres formees a partir de tels melanges
WO2008105595A1 (fr) 2007-02-28 2008-09-04 Young-Joon Moon Procédé de fabrication de blocs de polystyrène expansé ignifuges et de produits moulés associés

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE336469B (fr) * 1968-07-05 1971-07-05 Electrolux Ab
US5811470A (en) * 1996-05-06 1998-09-22 Albemarle Corporation Flame retardant styrenic polymers
EP1314753B1 (fr) * 2001-11-24 2006-12-27 Prometheus Developments Ltd. Composition ignifuge

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1479972A1 (de) 1962-01-26 1969-03-27 Basf Ag Verfahren zur Herstellung kombinierter Schaumstoffe
DE2352969A1 (de) 1973-10-23 1975-04-30 Basf Ag Verfahren zur herstellung von harten schaumstoffen mit hoher feuerwiderstandsdauer
EP0806451A1 (fr) 1996-05-06 1997-11-12 Albemarle Corporation Compositions de styrènes-polymères retardatrices de flamme
DE19910257A1 (de) 1999-03-08 2000-09-21 Schwenk Daemmtechnik Gmbh & Co Flammhemmend ausgerüstete Schaumstoffe auf Basis von Styrolpolymerisaten
GB2362586A (en) 2000-05-24 2001-11-28 Prometheus Developments Ltd Fire stable expanded polystyrene foam materials
US20040115455A1 (en) 2001-02-14 2004-06-17 Quist Per Ingmar Polymeric composite foam
WO2007048731A1 (fr) 2005-10-27 2007-05-03 Basf Se Film de resines aminoplastiques comprenant un papier impregne d’un melange de resines aminoplastiques comprenant des nanoparticules inorganiques
WO2007058736A1 (fr) 2005-11-12 2007-05-24 Dow Global Technologies Inc. Copolymeres de butadiene et de vinyle aromatique bromes, melanges de tels copolymeres avec un polymere de vinyle aromatique et mousses polymeres formees a partir de tels melanges
WO2008105595A1 (fr) 2007-02-28 2008-09-04 Young-Joon Moon Procédé de fabrication de blocs de polystyrène expansé ignifuges et de produits moulés associés

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
"Encyclopedia of Polymer Science and Technology", vol. 3, 2003, pages: 203 - 218
"Ullmann's Encyclopedia of Industrial Chemistry", vol. A2, 1985, VCH VERLAGSGESELLSCHAFT, pages: 115 - 141
J. I. G. CADOGAN; J. B. HUSBAND; H. MCNAB, J. CHEM. SOC. PERKIN TRANS., vol. 1, 1983, pages 1489 - 1495
M.G. ZIMIN; N. G. ZABIROV; V. SMIRNOV, ZHOURNAL OBSCHEI KHIMII, vol. 50, no. 1, 1980, pages 24 - 30
W. KUCHEN; H. BUCHWALD, CHEM. BER., vol. 91, 1958, pages 2871 - 2877

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2735584A1 (fr) * 2012-11-26 2014-05-28 Basf Se Mousse en résine en mélamine déformable à chaud avec matériau de remplissage à particules
WO2014080003A1 (fr) * 2012-11-26 2014-05-30 Basf Se Mousse de résine de mélamine thermoformable comportant une charge sous forme de particules
EP2743296A1 (fr) * 2012-12-11 2014-06-18 STO SE & Co. KGaA Procédé de fabrication d'un élément d'isolation ignifuge, élément d'isolation ainsi que l'utilisation d'un élément d'isolation
EP2873779A1 (fr) * 2013-11-13 2015-05-20 STO SE & Co. KGaA Procédé de fabrication d'un corps moulé à plusieurs couches et corps moulé à plusieurs couches destiné à l'isolation thermique de bâtiments
WO2015071214A1 (fr) * 2013-11-13 2015-05-21 Sto Se & Co. Kgaa Procédé de fabrication d'un élément moulé multicouche et élément moulé multicouche destiné à l'isolation thermique de bâtiments
RU2664080C1 (ru) * 2013-11-13 2018-08-15 Сто Се Унд Ко. Кгаа Способ изготовления многослойного формованного изделия, а также многослойное формованное изделие для теплоизоляции зданий
EP3530689A1 (fr) 2018-02-21 2019-08-28 Basf Se Pièce moulée et mélange et son procédé de fabrication
WO2019162304A1 (fr) 2018-02-21 2019-08-29 Basf Se Pièce moulée ainsi que mélange et procédé pour sa fabrication
WO2021032738A1 (fr) 2019-08-21 2021-02-25 Basf Se Particules de mousse à écoulement libre et moulages en mousse de particules ignifuges

Also Published As

Publication number Publication date
WO2011113795A3 (fr) 2011-12-01

Similar Documents

Publication Publication Date Title
EP1791896B1 (fr) Mousses polymeres ignifuges sans halogene
EP1819758B1 (fr) Polymeres styreniques expansibles, ignifuges et sans halogenes
WO2005056653A1 (fr) Piece moulee en mousse particulaire composee de granules polymeres expansibles contenant une charge
EP2513209A1 (fr) Mousses polymères ignifugées
WO2006058733A1 (fr) Granules de styrene polymere expansibles et mousse en particules presentant une conductivite thermique reduite
JP2013506009A (ja) 防炎性の発泡性重合体
EP2553008B1 (fr) Agents ignifuges
EP2658905B1 (fr) Systeme ignifugeant
AT511395B1 (de) Flammgeschützte expandierbare polymerisate
WO2010099020A2 (fr) Composition de polymère styrénique
WO2011113795A2 (fr) Mousse composite ignifugée
WO2006106120A1 (fr) Procede de production de particules de mousse de polystyrene de haute densite
EP2531552A2 (fr) Mousses polymères ignifugées contenant du phosphore et exemptes d'halogène
US20110230578A1 (en) Flame-retardant composite foam
KR20120034638A (ko) 입자상 발포성 폴리스타이렌 및 그의 제조방법
WO2006082233A1 (fr) Granules de polystyrene expansible (pse) ignifuges presentant un synergiste d'ignifugation dans le revetement
EP4077481B1 (fr) Copolymères et composés de moulage ignifuges
EP3755742B1 (fr) Pièce moulée et mélange et son procédé de fabrication
DE102004034527A1 (de) Verfahren zur Herstellung von expandierbaren Styrolpolymeren mit verbesserter Expandierbarkeit
EP2574614B1 (fr) Mousses polymères ignifuges dotées de moyens de protection contre les flammes sans halogène, contenant du phosphore et à base de sucre
DE102012217665A1 (de) Verfahren zur Herstellung von SAN-basierten expandierbaren Polymerpartikeln
WO2011095552A1 (fr) Agents ignifuges
EP2376562A2 (fr) Polystyrène expansible blanc à conductivité thermique améliorée
DE102004034515A1 (de) Selbstverlöschender Styrolpolymer-Partikelschaumstoff
EP2733165A1 (fr) Procédé pour la préparation de mousses de polystyrène retardateurs de flamme et libre d'halogène

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11708245

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11708245

Country of ref document: EP

Kind code of ref document: A2