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WO2013064444A1 - Compositions à base de polymères aromatiques de vinyle expansibles autoextinguibles - Google Patents

Compositions à base de polymères aromatiques de vinyle expansibles autoextinguibles Download PDF

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Publication number
WO2013064444A1
WO2013064444A1 PCT/EP2012/071330 EP2012071330W WO2013064444A1 WO 2013064444 A1 WO2013064444 A1 WO 2013064444A1 EP 2012071330 W EP2012071330 W EP 2012071330W WO 2013064444 A1 WO2013064444 A1 WO 2013064444A1
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Prior art keywords
polymer
weight
additive
vinyl aromatic
calculated
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Inventor
Antonio Ponticiello
Alessandra Simonelli
Maurizio Saiu
Riccardo Felisari
Olga Valentino
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Versalis SpA
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Versalis SpA
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • 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
    • C08J9/0019—Use of organic additives halogenated
    • 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
    • C08J9/0052—Organo-metallic 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
    • 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
    • C08J9/0066—Use of inorganic compounding ingredients
    • C08J9/0071—Nanosized fillers, i.e. having at least one dimension below 100 nanometers
    • C08J9/008—Nanoparticles
    • 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
    • C08J9/16—Making expandable particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/224—Surface treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products
    • C08J9/232—Forming foamed products by sintering expandable particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C08K5/57—Organo-tin compounds
    • C08K5/58—Organo-tin compounds containing sulfur
    • 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
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene

Definitions

  • the present invention relates to compositions of self-extinguishing expandable vinyl aromatic polymers and/or copolymers with an improved thermal stability.
  • the present invention also relates to a process for the preparation of said compositions. More specifically, the present invention relates to a composition based on expandable polymers and/or copolymers of styrene which contain a flame-retardant compound with an improved thermal stability.
  • Expandable vinyl aromatic polymers and/or copolymers in the text indicated as expandable vinyl aromatic polymers, and among these, in particular, expandable polymers and/or copolymers of styrene (EPS), are known products, long used for preparing articles which can be adopted in various applicative areas, among which, one of the most important is thermal insulation .
  • EPS styrene
  • These articles are obtained by first swelling (expanding) the polymer granules, in a closed environment, impregnated with a low-boiling fluid, for example an aliphatic hydrocarbon such as pentane or hexane, and then moulding the swollen particles charged inside a mould, by the contemporaneous effect of pressure and temperature.
  • a low-boiling fluid for example an aliphatic hydrocarbon such as pentane or hexane
  • the swelling of the particles is generally effected with vapour, or another gas, maintained at a temperature slightly higher than the glass transition temperature (Tg) of the polymer.
  • expandable vinyl aromatic polymers and, among these, expandable polystyrene are in the form of granules impregnated with the expanding agent and with a diameter of the granules generally ranging from 0.5 to 1.5 mm.
  • a number of additives are also homogeneously dispersed inside the granules, for improving the performances of the same granules and/or articles moulded therefrom.
  • the additives incorporated inside the granules there are flame-retardant additives.
  • the additives introduced into the polymer as flame- propagation retardants consist of at least one organic brominated product, for example hexabromocyclododecane, and a synergetic agent comprising, in the molecule, at least one thermolabile -0-0- or C-C bond, for example dicumyl peroxide or bicumyl.
  • Patent applications WO 2008/030399 and WO 2009/029290 relate to aromatic alkenyl polymeric foams containing a flame-retardant and a stabilizer.
  • WO 2008/030399 and WO 2009/029290 have the objective of protecting the flame-retardant from extensive decomposition during extrusion processes, and preventing the formation of surface defects on the polymeric foam, as lines, cuts, fractures and other irregularities .
  • WO 2008/030399 and WO 2009/029290 add a stabilizing additive to the polymeric composition, containing at least one allylophilic or dienophilic organotin compound selected from the group consisting of alkyl-tin thioglycolates , alkyl- tin mercaptopropionates, alkyl-tin mercaptides, alkyl-tin maleates and alkyl-tin di (alkylmaleates) , wherein the alkyl is selected from methyl, butyl and octyl groups.
  • the stabilizer is present in concentrations of up to 30% by weight with respect to the weight of the brominated flame-retardant .
  • WO 2008/030399 and WO 2009/029290 add an expanding agent to the polymeric composition, which includes water.
  • the expanding agent is therefore always a mixture of water and at least one compound selected from hydrocarbons, hydrofluorocarbides and fluorocarbides .
  • Patent application WO 2005/103133 relates to an additive that improves the thermal stability of a flame-retardant , which contains bromide atoms directly attached to one or more aliphatic or cycloaliphatic carbon atoms; said patent application also relates to the use of the flame-retardant additive in combination with expandable vinyl aromatic polymers.
  • the objective of WO 2005/103133 is to improve the thermal stability of brominated flame-retardants without having a negative impact from an environmental point of view.
  • WO 2005/103133 proposes a flame- retardant additive which comprises:
  • WO 2005/103133 preferably discloses a polymeric composition which comprises:
  • EPS expandable styrene thermoplastic polymer
  • At least one heat stabilizer which contains an acrylate or methacrylate thermoplastic polymer which melts within the range of 50°C to 150°C; iv) at least one component selected from:
  • a stabilizer containing tin such as for example dimethyltin bis ( isooctylmercapto- acetate) and analogous derivatives of dibutyltin and di-n-octyltin, alkyl-tin mercaptoalkanoates such as dibutyltin- ⁇ - mercaptopropionate, or
  • EP 1092 748 relates to an additive that improves the thermal stability of a brominated flame-retardant in thermoplastic polymers, such as expandable polystyrene or polystyrene foams.
  • EP 1092 748 The objective of EP 1092 748 is to increase the thermal stability of certain brominated flame- retardants becoming more effective also with respect to costs .
  • EP 1092 748 is a stabilizing additive containing a mixture composed of at least one alkyltin mercaptoalkanoate (B) , at least one zeolite (C) and at least one flame-retardant organo-brominated (A) selected from:
  • Said mixture is composed of from 0.01-0.08 parts by weight of B per parts by weight of A, and from 0.01- 0.35 parts by weight of C per parts by weight of A.
  • Patent application GB 1,020,291 relates to organo- tin compounds suitable as stabilizers against the thermal degradation of synthetic resins containing chlorine such as vinyl chloride polymers and copolymers .
  • the objective of GB 1, 020, 291 is to oppose the thermal degradation of synthetic resins containing chlorine, such as vinyl chloride polymers, by means of a composition containing vinyl chloride polymers (PVC) and di-alkyl organotin compounds.
  • synthetic resins containing chlorine such as vinyl chloride polymers
  • Patent application GB 743,304 relates to organic derivatives of tetravalent tin, among which alkyltin mercapto esters, which can be used as stabilizers of high-molecular-weight halogenated organic compounds. These derivatives are specifically used as stabilizers of polyvinyl resins containing chlorides.
  • GB 743,304 discloses the compounds di-n-butyl tin-S , S ' -di (mercapto ethanol) adipate and mono-isopropyl tin dimercapto ethanol terephthalate.
  • WO 2009/138474 relates to high-purity mono-alkyl tin compounds and their use as stabilizers of polymers and copolymers containing chlorine.
  • the objective of WO 2009/138474 is to stabilize polymers containing chlorine using compounds with improved toxicological properties and specifically a polymeric composition containing a chlorinated polymer (PVC) and a high- purity mono-alkyl tin mercapto ester, or a mixture containing a mono-alkyl tin as major component and a di-alkyl tin and/or tri-alkyl tin as minor components, as these are toxic substances.
  • PVC chlorinated polymer
  • WO 2009/138474 discloses compounds having the formula RSn(T) 3 , R 2 Sn(T) 2 , R 3 Sn(T) wherein R is a mono-alkyl group and T can also be a mercapto ester.
  • Specific compounds disclosed are mono-methyl tin [tris (2- ethylhexylmercaptoacetate) ] , mono-n-butyl tin [tris (2- ethylhexylmercaptoacetate)], mono-n-octyl tin [tris (2- ethylhexylmercaptoacetate) ] .
  • the compounds described in WO 2009/138474 confer thermal stability to the chlorinated polymers and copolymers with which they are mixed .
  • the melt In order to have optimum conditions of fluidity and consequently miscibility, moreover, the melt must be kept at a high temperature, for example from 170°C to 300°C. Under these conditions, some of the additives, and among these the brominated organic compound, tend to degrade and create undesired by-products which remain incorporated in the polymeric mass.
  • the brominated organic compound in particular tends to release bromine or hydrobromic acid which may not only create problems of an environmental nature, but can also damage/corrode the mixing equipment. Furthermore, the decomposition of the brominated compound reduces the self-extinguishing properties of the end-material compelling producers to increase the quantity of this additive in the formulations .
  • the Applicant has now found a further additive, to be added to an expandable polymeric composition in the molten state and comprising a vinyl aromatic polymer and/or copolymer.
  • This additive is capable of inhibiting the degradation of brominated organic compounds present in the polymeric composition, when they are subjected to a high temperature, without creating a deterioration in the chemical/physical properties of the resulting expandable granules.
  • the present invention therefore relates to a composition based on self-extinguishing expandable vinyl aromatic polymers, which comprises:
  • a a polymer obtained by the polymerization of one or more vinyl aromatic monomers present in a variable quantity ranging from 50 to 100% by weight, and a monomer copolymerizable with the vinyl aromatic monomers, homogeneously englobed in the polymer in an amount ranging from 0% to 50% by weight;
  • At least one expandable system in an amount ranging from 3 to 10% by weight, calculated with respect to the polymer (a) ;
  • At least one flame-retardant additive in an amount ranging from 0.005 to 5% by weight, calculated with respect to the polymer (a) , and containing at least 30% by weight of bromine, said amount being calculated with respect to the flame-retardant additive ;
  • Athermanous additive selected from carbon-black, a graphite, a carbon coke in particle form and mixtures thereof;
  • composition is characterized in that it contains a stabilizing additive including at least one alkyl tin mercapto ester having a purity higher than or equal to 95%.
  • An object of the present invention relates to a composition based on self-extinguishing expandable vinyl aromatic polymers, which comprises:
  • a a polymer obtained by the polymerization of one or more vinyl aromatic monomers present in a variable quantity ranging from 50 to 100% by weight, and a monomer copolymerizable with the vinyl aromatic monomers, homogeneously englobed in the polymer in an amount ranging from 0% to 50% by weight;
  • At least one expandable system in an amount ranging from 3 to 10% by weight, calculated with respect to the polymer (a) ;
  • At least one flame-retardant additive in an amount ranging from 0.005 to 5% by weight, calculated with respect to the polymer (a) , and containing at least 30% by weight of bromine, said amount being calculated with respect to the flame-retardant additive ;
  • Athermanous additive selected from carbon-black, a graphite, a carbon coke in particle form and mixtures thereof;
  • composition is characterized in that it contains a stabilizing additive including at least one alkyl tin mercapto ester having a purity higher than or equal to 95%.
  • An object of the present invention also relates to an expandable composition based on vinyl aromatic polymers having self-extinguishing properties, said composition comprising:
  • A a polymer obtained by the polymerization of one or more vinyl aromatic monomers present in a variable quantity ranging from 50 to 100% by weight, and a monomer copolymerizable with the vinyl aromatic monomers, homogeneously englobed in the polymer in an amount ranging from 0% to 50% by weight;
  • B at least one expandable system in an amount ranging from 3 to 10% by weight, calculated with respect to the polymer (A) ;
  • a flame-retardant additive in an amount ranging from 0.005 to 5% by weight, calculated with respect to the polymer (A) , and containing at least 30% by weight of bromine, said amount being calculated with respect to the flame-retardant additive;
  • D a synergetic additive containing a C-C or C-O-O-C thermolabile bond in an amount ranging from 0.001% to 2% by weight, calculated with respect to the polymer (A) ;
  • composition is characterized in that it contains a stabilizing additive including at least one mono-alkyl tin mercapto ester having a purity higher than or equal to 95%.
  • the stabilizing additives are capable of inhibiting the thermal degradation of the flame-retardant (or anti-flame additive) also in the presence of the synergetic additive .
  • the stabilizing additive is preferably present in an amount ranging from 0.001% by weight to 3% by weight, more preferably in an amount ranging from 0.01% by weight to 1% by weight, calculated with respect to the polymer (a) or (A) of the compositions described and claimed.
  • the stabilizer preferably comprises at least one mono-alkyl tin mercapto ester, more preferably a mono- alkyl tin acetate, and even more preferably the stabilizing additive is selected from mono-octyltin tris alkyl mercaptoacetate and mono-octyltin tris (2- ethylhexylmercaptoacetate, and mixtures thereof.
  • the alkyl tin mercapto ester compounds and in particular mono-alkyl tin mercapto ester compounds, must have a purity higher than 95%, and preferably higher than 99%.
  • the high degree of purity allows these stabilizers to be classified as harmful, unlike the known conventional stabilizers which are classified as toxic, such as for example tin dibutyl maleate.
  • the stabilized flame-retardant composition, object of the present invention consequently has an improved environmental impact with respect to the known stabilized flame-retardant compositions.
  • the compound mono- octyl tin tris 2-ethylhexylmercaptoacetate known as Thermolite 895 and produced by ARKEMA, under item 2 of the SAFETY DATA SHEET (Hazard Identification Classification - Regulation EC N°1272/2008) this is classified as Xi; R38/N; R50/53.
  • Baerostab MS is classified as T/N; R60, R61, R22, R23, R36, R48/25, R68, R50/53. Consequently, mono-octyl tin tris 2-ethylhexylmercaptoacetate) has a better safety profile with respect to a traditional additive such as dibutyl tin maleate.
  • vinyl aromatic polymers and/or (co) polymers refers to polymeric products having a weight average molecular weight (MW) ranging from 50,000 to 300,000, preferably ranging from 70,000 to 220,000.
  • MW weight average molecular weight
  • These vinyl aromatic polymers can be obtained by polymerizing a mixture of monomers which comprises from 50 to 100% by weight, preferably from 75 to 98% by weight, of one or more vinyl aromatic monomers, and at least one monomer copolymerizable with the vinyl aromatic monomers, homogeneously englobed in the polymer in a quantity ranging from 0 to 50% by weight, preferably from 2 to 25% by weight.
  • the vinyl aromatic monomers can be selected from those corresponding to the following general formula:
  • R is a hydrogen or a methyl group
  • n is zero or an integer ranging from 1 to 5
  • Y is a halogen, preferably selected from chlorine or bromine, or an alkyl or alkoxyl radical having 1 to 4 carbon atoms.
  • vinyl aromatic monomers having the general formula (I) are: styrene, -methylstyrene, methylstyrene, ethylstyrene, butylstyrene, dimethylstyrene, mono-, di-, tri-, tetra- and penta- chlorostyrene, bromostyrene, methoxystyrene, acetoxystyrene .
  • Preferred vinyl aromatic monomers are styrene and a-methylstyrene.
  • (I) can be used alone or in a mixture up to 50% by weight, preferably from 2 to 25% by weight, with other co-polymerizable monomers.
  • these monomers are (meth) acrylic acid, C1-C4 alkyl esters of (meth) acrylic acid such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isopropyl acrylate, butyl acrylate, amides and nitriles of (meth) acrylic acid such as acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, butadiene, ethylene, divinyl benzene, maleic anhydride.
  • Preferred co-polymerizable monomers are acrylonitrile, methyl methacrylate.
  • Preferred flame-retardant agents for the present invention are aliphatic, cycloaliphatic, aromatic compounds, for example C6 _ Ci8, brominated compounds such as hexabromocyclododecane (EBCD) , pentabromomonochlorocyclohexane, pentabromophenyl allyl ether, bis-tetrabromobisphenol-A allyl ether (known on the market as "Chemtura BE51", produced by Chemtura) , tetrabromobisphenol A bis (2,3 dibromopropyl ether) (known on the market as "Chemtura PE-68”) .
  • EBCD hexabromocyclododecane
  • pentabromomonochlorocyclohexane pentabromophenyl allyl ether
  • bis-tetrabromobisphenol-A allyl ether known on the market as "Chemtura BE51", produced by Chemtura
  • the flame- retardant additives can be present in the polymeric composition, object of the present invention, in a quantity ranging from 0.005% by weight to 5% by weight, preferably ranging from 0.1% by weight to 4% by weight, said quantity being calculated with respect to the polymer (a) or (A) of the compositions described and claimed .
  • the flame-retardant additives used for the purposes of the present invention contain at least 30% by weight of bromine, preferably from 50% to 90% by weight of bromine .
  • Preferred synergetic additives used in the present invention can be selected from dicumyl peroxide (DCP) , cumene hydroperoxide, 3, 4-dimethyl-3, 4-diphenyl hexane, 2 , 3-dimethyl-2 , 3-diphenyl butane, 3, 6, 9-triethyl-3, 6, 9- trimethyl-1 , 4 , 7-triperoxynonane, and poly ( 1 , 4-diiso- propylbenzene) .
  • DCP dicumyl peroxide
  • cumene hydroperoxide 3, 4-dimethyl-3, 4-diphenyl hexane, 2 , 3-dimethyl-2 , 3-diphenyl butane, 3, 6, 9-triethyl-3, 6, 9- trimethyl-1 , 4 , 7-triperoxynonane, and poly ( 1 , 4-diiso- propylbenzene) .
  • These synergetic additives are used in the present invention in preferred quantities
  • the expanding agents can be liquid substances with a boiling point ranging from 10 to 80°C, preferably from 20 to 60°C.
  • Preferred expanding agents are aliphatic or cycloaliphatic hydrocarbons containing 3 to 6 carbon atoms such as n-pentane, iso-pentane, cyclopentane or mixtures thereof; halogenated derivatives of aliphatic hydrocarbons containing from 1 to 3 carbon atoms, such as dichlorodifluoromethane, 1 , 2 , 2-trifluoroethane and 1, 1, 2-trifluoroethane; carbon dioxide.
  • the expanding system is present in a quantity varying from 3% to 10% by weight, said quantity being calculated with respect to the polymer (a) or (A) of the compositions described and claimed.
  • additives capable of forming bonds of both the weak type (for example hydrogen bridges) and strong type (for example acid- base adducts) can be used with the expanding agent.
  • These additives are preferably selected from methyl alcohol, isopropyl alcohol, dioctylphthalate, dimethyl carbonate, derivatives containing an amine group.
  • the athermanous additive can be selected from a carbon black, a graphite, a carbon coke in particle form and mixtures thereof.
  • the carbon black can be present in a quantity ranging from 0.01% to 20% by weight, preferably from 0.05% to 20% by weight, more preferably 0.1% to 10% by weight, said quantity being calculated with respect to the polymer (a) or (A) of the compositions described and claimed.
  • the graphite can be present in a quantity ranging from 0.01% to 20% by weight, preferably from 0.05% to 8% by weight, more preferably 0.1% to 10% by weight, said quantity being calculated with respect to the polymer (a) or (A) of the compositions described and claimed.
  • the carbon coke can be present in a quantity ranging from 0.01% to 20% by weight, more preferably 0.1% to 10% by weight, calculated with respect to the polymer (a) or (A) of the compositions described and claimed.
  • the carbon black preferably has an average diameter (d50), measured with a laser granulometer, ranging from 30 to 1,000 nm.
  • the graphite can be selected from natural, synthetic, expanded, expandable graphite, and mixtures thereof.
  • the graphite particles can have a maximum dimension (d50), measured with a laser granulometer, ranging from 0.05 ⁇ to 100 ⁇ , preferably from 1 ⁇ to 8 ⁇ , with a surface area, measured according to ASTM D-3037-89 (BET), ranging from 5 to 30 m 2 /g.
  • the carbon coke is in particle form with an average diameter of the particles (d50) ranging from 0.5 ⁇ to 100 ⁇ , preferably from 2 ⁇ to 8 ⁇ , and a surface area, measured according to ASTM D-3037- 89 (BET) ranging from 5 to 200 m 2 /g, preferably from 8 to 50 m 2 /g.
  • d50 average diameter of the particles
  • BET surface area
  • the expandable compositions, object of the present invention contain an athermanous additive, it is possible to obtain expanded granules with a reduced density and with an improved thermal insulation capacity.
  • the end-products containing these compositions and specifically containing 5% of calcined coke 4023 have a thermal conductivity of 30.5 mW/m*K, at a density of 16 g/1.
  • Traditional end-products, without athermanous fillers, have a thermal conductivity of 38 mW/m*K, at a density of 16 g/1 (measured according to the method ISO 8301) .
  • additives can be added to the compositions, object of the present invention, such as additives generally used with traditional vinyl aromatic polymers such as pigments, stabilizing agents, antistatic agents and detaching agents.
  • a further object of the present invention relates to a process for preparing, in continuous mass, the composition described and claimed in the present text, based on self-extinguishing expandable vinyl aromatic- based polymers containing an athermanous additive and at least one alkyl tin mercapto ester having a purity higher than 95%.
  • Said process comprises the following phases :
  • a further object of the present invention relates to a process for preparing, in continuous mass, the composition described and claimed in the present text, based on self-extinguishing expandable vinyl aromatic- based polymers containing at least one mono alkyl tin mercapto ester having a purity higher than or equal to 95%. Said process comprises the following phases:
  • compositions, object of the present invention can be mixed by means of static or dynamic elements, and granulated in a device which comprises a die, a cutting chamber and a cutting system.
  • the flame-retardant additive is added in a quantity ranging from 0.005 by weight, calculated on the polymer (a) or (A) of the compositions, object of the present invention, and contains at least 30% by weight, preferably from 50% to 90% by weight, of bromine.
  • the synergetic additive of the flame-retardant additive contains a C-C or C-O-O-C thermolabile bond; said additive is added in a quantity ranging from 0.001% a 2% by weight, calculated on the polymer (a) or (A) of the compositions, object of the present invention.
  • step (i) can be effected by feeding the polymeric granule already formed, possibly mixed with processing waste-products, into an extruder.
  • the single components are mixed therein and the polymeric part is subsequently melted and the additives and expanding agent are then added.
  • the polymer can be used already in the molten state, coming directly from the polymerization plant (process in solution) , in particular from the relative devolatilization unit.
  • the molten polymer is fed to suitable devices, for example an extruder or a static mixer, where it is mixed with all the additives and then with the expanding agent, and it is subsequently extruded to give the expandable granulate, object of the present invention.
  • expandable granules having a spherical form can be obtained, with an average diameter ranging from 0.2 mm to 2 mm.
  • the expanded beads allow expanded articles to be obtained, having a density ranging from 5 g/1 to 50 g/1, preferably from 10 g/1 to 25 g/1.
  • said expanded articles have an optimum thermal insulation capacity, expressed by a thermal conductivity ranging from 25 mW/mK to 50 mW/mK, preferably from 30 mW/mK to 45 mW/mK.
  • the thermal conductivity measurement is carried out at 10°C according to the method DIN 13163 on end-products obtained from blocks having a density of 15 g/1.
  • the granules of the polymeric composition can be annealed at a temperature lower than or equal to the glass transition temperature (Tg) or slightly higher, for example the Tg increased by up to 8°C, possibly under pressure.
  • Tg glass transition temperature
  • the expandable granules obtained can be subjected to pre-treatment which is normally applied to conventional expandable granules and which essentially consists in:
  • a liquid antistatic agent such as amines, ethoxylated tertiary alkylamines, ethylene oxide/propylene oxide copolymers
  • said coating essentially consisting of a mixture of mono-, di- and tri-esters of glycerine (or other alcohols) with fatty acids, and metal stearates such as zinc and/or magnesium stearate.
  • Said agent allows the coating to adhere and facilitates the screening of the granules prepared in suspension.
  • brominated compounds such as, for example, hexabromocyclododecane, which give the polymers self-extinguishing properties, when subjected to high temperatures, (higher than 180°C), can release hydrobromic acid as a result of thermal decomposition processes.
  • high temperatures high than 180°C
  • hydrobromic acid hydrobromic acid
  • the addition of the stabilizing additive in the compositions described and claimed in the present text allows the mechanical characteristics in compression, of the resulting expanded articles to be enhanced, as also illustrated in the examples provided in the present text.
  • the dosage of the tin- based thermal stabilizer, object of the present invention surprisingly also significantly enhances the mechanical properties in compression, of the expanded test samples containing the compositions described and claimed in the present text.
  • the evaluations of the mechanical characteristics in compression were effected on the single test samples of expanded material (polystyrene) , using a Zwick I 2020 tensometer, according to the method EN 826.
  • a sample of flame-retardant additive is placed in a 10 ml sealed vial, heated to the temperature selected and subjected to a stream of nitrogen (60 ml per minute) which removes the hydrobromic acid possibly released.
  • the nitrogen flow carries the hydrobromic acid (and other decomposition products of the sample) into an aqueous solution which is basic due to sodium hydroxide and whose pH is measured by means of a glass electrode connected to an automatic Metrohm 736 GP titrator arranged with a burette filled with a solution of NaOH with a known titre.
  • the acid in gas phase carried by the nitrogen flow, neutralizes the sodium hydroxide and lowers the pH of the solution.
  • the titrator activates the burette by supplying NaOH to such a degree as to keep the pH constant.
  • the volume of titrating product is registered in continuous by means of a computer.
  • the quantity of hydrobromic acid released by the sample is obtained from the volume and titre of the NaOH solution used.
  • the reactive polymeric composition having a conversion of 72%, is heated to 240°C and subsequently fed to the devolatilizer to remove the solvent and residual monomer.
  • the resulting composition has a glass transition temperature of 104°C, a melt flow index (MFI 200°C, 5 kg) of 8 g/10', a molecular weight Mw of 200, 000 g/mol and a Mw/Mn ratio of 2.8, wherein Mw is the weight average molecular weight and Mn is the number average molecular weight.
  • composition thus obtained is collected in a heated tank and fed to a heat exchanger to lower its temperature to 190°C.
  • the granulation pressure is 5 bar and the shear deformation rate is selected so as to obtain granules having an average diameter of 1.2 mm.
  • Water is used as spray liquid and nitrogen as carrier gas.
  • the ratio between the flow-rate of the water sprayed and the flow-rate of the polymeric mass is 30 and the ratio between the nitrogen and polymeric mass is 20.
  • the temperature of the water is 40°C.
  • the resulting granulated beads are dried with a centrifugal drier and then covered with a coating.
  • the coating is prepared by adding to the same, 3 parts of glyceryl monostearate, 1 part of zinc stearate and 0.2 parts of glycerine per 1,000 parts of dried granulated beads.
  • the coating additives are mixed with the granulate by means of a continuous worm-screw mixer.
  • the beads are then expanded and moulded.
  • the thermal conductivity of the end-products obtained proved to be 34.7 mW/mK at 16.4 g/1 (according to the method ISO 8301) .
  • Some sheets obtained from the end-products were introduced into an oven at 70°C for 2 days: test samples were then collected (9cm x 19cm x 2cm) for the fire behaviour test according to the standard DIN 4102. The test-samples passed the test.
  • the expandable beads thus obtained are analyzed to quantify the bromides present in the polymer.
  • the bromide content in the EPS beads is an index of the degradation undergone by the organobrominated agent introduced into the polymer as flame-retardant .
  • the EPS beads thus obtained have 350 ppm of bromides.
  • the cell structure evaluated on the expanded end-products proved to be homogeneous .
  • the mechanical characteristics in compression were tested with a Zwick I 2020 tensometer, according to the method EN 826. Two test-samples (100 x 100 x 50 mm) were collected from the expanded end-products and tested at 5 mm/min. The average value at 10% of compression proved to be the following: 93 Kpa (pressure at which the test-sample becomes deformed) at a density of 16.4 g/1.
  • Example 1 was repeated, without the dosage of high- purity monoalkyl tin mercapto ester.
  • the polymeric composition containing calcined coke is collected in a tank and cooled to a temperature of 190°C. 129.1 parts of polystyrene N2982, 15.7 parts of HBCD Saytex HP 900 and 5.2 parts of Perkadox 30 (total: 150 parts) are then dosed in a twin-screw extruder. 47 parts of expanding agent consisting of a mixture of n-pentane (75%) and iso-pentane (25%) are subsequently added. The composition thus obtained is added to 850 parts of the polymeric composition, as in Example 1. The mixture obtained then reaches the die where expandable granulates with an average diameter of about 1.2 mm are obtained. These granules are then dried and treated with the coating. The types and quantity of coating additives used are the same as those of Example 1. The beads produced are expanded and moulded.
  • the thermal conductivity measured on the end- products obtained proved to be 34.6 mW/mK at a density of 16.2 g/1.
  • the expandable polymer beads are dried and coating powders are then added to these.
  • the coating additives and quantities dosed are the same as those indicated in Example 1.
  • the granulates produced are expanded and moulded.
  • the end-products obtained have a thermal conductivity of 34.4 mW/mK at a density of 16.3 g/1.
  • a series of test samples collected from the expanded end- products (9cm x 19cm x 2cm) were conditioned in an oven at 70°C for 2 days and subjected to the fire behaviour test according to the standard DIN 4102. The test- samples passed the test.
  • the analysis, effected on the dried EPS beads without a coating confirms the presence of 470 ppm of bromides.
  • the cell structure evaluated on the expanded end- products proved to be homogeneous.
  • the resulting composition has a glass transition temperature of 104°C, a melt flow index (MFI 200°C, 5 kg) of 8 g/10', a molecular weight Mw of 200, 000 g/mol and a Mw/Mn ratio of 2.8, wherein Mw is the weight average molecular weight and Mn is the number average molecular weight.
  • composition thus obtained is collected in a heated tank and fed to a heat exchanger to lower its temperature to 190°C.
  • the granulation pressure is 5 bar and the shear deformation rate is selected so as to obtain granules having an average diameter of 1.2 mm.
  • Water is used as spray liquid and nitrogen as carrier gas.
  • the ratio between the flow-rate of the water sprayed and the flow-rate of the polymeric mass is 30 and the ratio between the nitrogen and polymeric mass is 20.
  • the temperature of the water is 40°C.
  • the resulting granulated beads are dried with a centrifugal drier and then covered with a coating.
  • the coating is prepared by adding to the same, 3 parts of glyceryl monostearate, 1 part of zinc stearate and 0.2 parts of glycerine per 1,000 parts of dried granulated beads.
  • the coating additives are mixed with the granulate by means of a continuous worm-screw mixer.
  • the beads are then expanded and moulded.
  • the thermal conductivity of the end-products obtained proved to be 36.4 mW/mK at 16.5 g/1 (according to the method ISO 8301) .
  • test samples were then collected (9cm x 19cm x 2cm) for the fire behaviour test according to the standard DIN 4102. The test-samples passed the test.
  • the expandable beads obtained were analyzed to quantify the bromides present in the polymer.
  • the bromide content in the EPS beads indicates the degradation undergone by the organobrominated agent introduced into the polymer as flame-retardant .
  • the EPS beads thus obtained have 140 ppm of bromides.
  • the cell structure evaluated on the expanded end-products proved to be homogeneous.
  • the mechanical characteristics in compression were tested with a Zwick I 2020 tensometer, according to the method EN 826. Two test-samples (100 x 100 x 50 mm) were collected from the expanded end-products and tested at 5 mm/min. The average value at 10% of compression proved to be the following: 98 Kpa (pressure at which the test-sample becomes deformed) at a density of 16.5 g/1.
  • Example 1 was repeated, dosing the same quantity of stabilizing agent (high-purity monoalkyl tin mercapto ester) , but the calcined coke was substituted with carbon black TN 990 UP produced by Cancarb.
  • stabilizing agent high-purity monoalkyl tin mercapto ester
  • Example 2 the polymeric composition containing carbon black then reaches the die where expandable granulates with an average diameter of about 1.2 mm are obtained. These granules are then dried and treated with the coating.
  • the types and quantity of coating additives used are the same as those of Example 1. The beads produced are expanded and moulded.
  • the thermal conductivity measured on the end- products obtained proved to be 35.3 mW/mK at a density of 16.7 g/1.
  • the average value at 10% of compression proved to be the following: 93 Kpa at a density of 16.7 g/1.
  • Example 1 was repeated, dosing the same quantity of stabilizing agent (high-purity monoalkyl tin mercapto ester) , but the calcined coke was substituted with UF2 graphite, produced by Graphit Kropfmiihl AG.
  • stabilizing agent high-purity monoalkyl tin mercapto ester
  • Example 2 the polymeric composition containing graphite then reaches the die where expandable granulates with an average diameter of about 1.2 mm are obtained. These granules are then dried and treated with the coating.
  • the types and quantity of coating additives used are the same as those of Example 1.
  • the beads produced are expanded and moulded .
  • the thermal conductivity measured on the end- products obtained proved to be 34.1 mW/mK at a density of 16.2 g/1.
  • the average value at 10% of compression proved to be the following: 92 Kpa at a density of 16.2 g/1.
  • Example 2 was repeated, substituting the stabilizing agent Thermolite 895 (high-purity monoalkyl tin mercapto ester) with a tin-based stabilizer of the traditional type (dibutyl tin maleate - Baerostab MS produced by Baerlocher) .
  • Example 2 the polymeric composition containing dibutyl tin maleate reaches the die where expandable granulates with an average diameter of about 1.2 mm are obtained. These granules are then dried and treated with the coating.
  • the types and quantity of coating additives used are the same as those of Example 2. The beads produced are expanded and moulded.
  • the thermal conductivity measured on the end- products obtained proved to be 36.6 mW/mK at a density of 16.4 g/1.
  • Table 1 indicates the results of the tests effected with the various types of athermanous agents and 5 stabilizing agents.
  • K is the thermal conductivity (ISO 8301) measured in [mW/mK]
  • P is the compression measured in [Kpa] (EN826) .

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Abstract

Cette invention concerne une composition à base de polymères aromatiques de vinyle expansibles autoextinguibles qui comprend : a) un polymère obtenu par polymérisation d'un ou de plusieurs monomères aromatiques de vinyle présents en une quantité allant de 50 à 100 % en poids, et un monomère copolymérisable avec les monomères aromatiques de vinyle, incorporé de manière homogène au polymère en une quantité allant de 0 à 50 % en poids ; b) au moins un système d'expansion en une quantité allant de 3 à 10 % en poids, calculée par rapport au polymère (a) ; c) au moins un additif ignifugeant en une quantité allant de 0,005 à 5 % en poids, calculée par rapport au polymère (a), et contenant au moins 30 % en poids de brome, ladite quantité étant calculée par rapport à l'additif ignifugeant ; d) au moins un additif synergique contenant une liaison thermolabile C-C ou C-O-O-C en une quantité allant de 0,001 à 2 % en poids, calculée par rapport au polymère (a) ; et e) au moins un additif athermane choisi parmi le noir de carbone, un graphite, un coke sous forme particulaire et leurs mélanges ; ladite composition étant caractérisée en ce qu'elle contient un additif de stabilisation comprenant au moins un mercapto-ester d'alkyle stannique ayant une pureté supérieure ou égale à 95 %.
PCT/EP2012/071330 2011-11-02 2012-10-29 Compositions à base de polymères aromatiques de vinyle expansibles autoextinguibles Ceased WO2013064444A1 (fr)

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* Cited by examiner, † Cited by third party
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WO2018069185A1 (fr) 2016-10-10 2018-04-19 Total Research & Technology Feluy Polymères aromatiques de vinyle expansibles améliorés
WO2018069178A1 (fr) 2016-10-10 2018-04-19 Total Research & Technology Feluy Polymères aromatiques de vinyle expansibles améliorés
WO2018069186A1 (fr) 2016-10-10 2018-04-19 Total Research & Technology Feluy Polymères aromatiques vinyliques expansibles améliorés
WO2021043552A1 (fr) 2019-09-04 2021-03-11 Total Research & Technology Feluy Polymères aromatiques vinyliques expansibles présentant une ininflammabilité améliorée
US11447613B2 (en) 2016-05-11 2022-09-20 Owens Corning Intellectual Capital, Llc Polymeric foam comprising low levels of brominated flame retardant and method of making same

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GB1020291A (en) 1961-05-09 1966-02-16 Pure Chem Ltd Improvements in and relating to organic stabiliser compositions
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US11447613B2 (en) 2016-05-11 2022-09-20 Owens Corning Intellectual Capital, Llc Polymeric foam comprising low levels of brominated flame retardant and method of making same
WO2018069185A1 (fr) 2016-10-10 2018-04-19 Total Research & Technology Feluy Polymères aromatiques de vinyle expansibles améliorés
WO2018069178A1 (fr) 2016-10-10 2018-04-19 Total Research & Technology Feluy Polymères aromatiques de vinyle expansibles améliorés
WO2018069186A1 (fr) 2016-10-10 2018-04-19 Total Research & Technology Feluy Polymères aromatiques vinyliques expansibles améliorés
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