EP2699634A1 - Polymères expansibles à retard de flamme - Google Patents

Polymères expansibles à retard de flamme

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Publication number
EP2699634A1
EP2699634A1 EP12720389.1A EP12720389A EP2699634A1 EP 2699634 A1 EP2699634 A1 EP 2699634A1 EP 12720389 A EP12720389 A EP 12720389A EP 2699634 A1 EP2699634 A1 EP 2699634A1
Authority
EP
European Patent Office
Prior art keywords
oxa
dihydro
expandable
polymers
flame retardant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP12720389.1A
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German (de)
English (en)
Inventor
Roman Eberstaller
Gerhard Hintermeier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sunpor Kunststoff GmbH
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Sunpor Kunststoff GmbH
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Publication date
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Publication of EP2699634A1 publication Critical patent/EP2699634A1/fr
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Classifications

    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34928—Salts
    • 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
    • C08J9/0033—Use of organic additives 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
    • 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
    • C08J9/16—Making expandable particles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/10—Organic materials containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials 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
    • 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
    • C08J2325/06—Polystyrene

Definitions

  • the present invention relates to flame-retardant, at least one blowing agent-containing, expandable polymers.
  • the invention further relates to a process for the preparation of these polymers, further with this flame retardants protected polymer foams and processes for their preparation, and the particular use of the above flame retardants in expandable polymers and polymer foams.
  • EPS expandable polystyrene
  • XPS expanded polystyrene
  • Polystyrene homo- and copolymers are predominantly rendered flame-retardant with halogen-containing, in particular brominated organic compounds such as hexabromocyclododecane (HBCD).
  • HBCD hexabromocyclododecane
  • halogen-free flame retardants As an alternative, there are many halogen-free flame retardants. However, halogen-free flame retardants generally have to be used in significantly higher amounts in order to achieve the same flameproofing effect of the halogen-containing flame retardants.
  • halogen-free flame retardants which can be used in compact thermoplastic polymers are often not used in the same way in polymer foams, since they either interfere with the foaming process or influence the mechanical and thermal properties of the polymer foam.
  • the high flame retardant can also reduce the stability of the suspension and thus interfere with the production process or affect.
  • WO 2006/027241 describes a halogen-free flame retardant for polymer foams based on 9,10-dihydro-9-oxa-10-phosphaphenantrene-10-oxide (6H-dibenz [c, e] -oxaphosphorine 6-oxide, DOPO , CAS [35948-25-5]) and its derivatives.
  • This flame retardant can be used, but high concentrations must be added and at the same time DOPO shows a strong softening effect, so that with sufficient flame retardant effect required in most European countries for construction products requirements for mechanical stability, is no longer achievable.
  • US 5,811 1,470 discloses a flame retardant system consisting of an organic halogen-free phosphorus compound and elemental sulfur in styrene polymers.
  • Polymer foams, in particular polystyrene foams are not considered.
  • elemental sulfur has the disadvantage that in the production of expandable polymers, their processing and in the final product, the resulting in side reactions of organic sulfur compounds represent an intense odor.
  • a further object of the invention is to provide a halogen-free flame-retardant, but qualitatively corresponding, polymer foam with advantageous fire behavior, non-irritating olfactory properties as well as good mechanical properties and an advantageous production method therefor.
  • the polymer or the polymer foam and the stringent requirements for fire resistance for example Construction applications met, such as the B2 small burner test according to DIN 4102-2 or the small burner test according to EN 1 1925-2.
  • Melaminium thiosulfate is contained as Flammtiksynergist as part of a flame retardant composition or in combination with at least one flame retardant.
  • melamine (ium) thiosulphate which in itself does not exhibit any flameproofing effect even in higher concentrations, in combination with a flame retardant, for example with phosphorus compounds, produces a surprisingly good increase in the flame retardant effect.
  • the total amount of flame retardant can be reduced, resulting in a variety of benefits, i.a. in the production process, in the costs, the mechanical properties of the product, etc. Above all, the foaming process and the mechanical properties of the foam are not appreciably affected, resulting in a high quality product.
  • melaminium thiosulfate in an amount of 1 to 25 wt.%, In particular in an amount of 2 to 15 wt%, based on the total weight of the polymer or of the granules thus obtained is included.
  • phosphorus compound is contained as a flame retardant, wherein the phosphorus compound is selected from elemental phosphorus, in particular red phosphorus, and / or at least one inorganic phosphorus compound or hydrolysates or salts thereof and / or at least an organic phosphorus compound represented by the following general formula (I) or (II) or hydrolyzates or salts thereof:
  • radicals R 1f R 2 and R 3 each independently represent organic or inorganic radicals.
  • phosphorus compounds is taken to mean or subsume elemental phosphorus as well as organic and inorganic phosphorus compounds and / or phosphorus-containing compounds and hydrolyzates or salts thereof. Elemental phosphorus occurs in four allotropic modifications as white, red, black and purple phosphorus. Each of these basic types forms different crystal structures, which also results in differences in physical properties and reactivities. As a flame retardant, the red phosphorus is most advantageously used.
  • inorganic phosphorus compounds are advantageously the (poly) phosphates, such as non-condensed salts of phosphorous acid or condensed salts, such as ammonium phosphate and ammonium polyphosphate in question.
  • the substituents or radicals R 1t R 2 and R 3 of the organic phosphorus compound are independent of each other and may be the same or different or even completely absent.
  • the radicals R may preferably represent each independently -H, substituted or unsubstituted C 1 -C 20 alkyl, (C ⁇ alkenyl, C 3 -C 8 cycloalkyl, C 6 - C 8 aryl, C 7 -C 30 -alkylaryl, Ci-C 8 -alkoxy or Ci-C 8 -alkylthio, or -OH or -SH and alkali metal, alkaline earth metal, ammonium or phosphonium salts thereof.
  • alkyl portion of the optional substituents R of the phosphorus compounds according to formula (II) is understood as meaning both saturated and unsaturated aliphatics which may be unbranched or branched, with unsaturated groups being preferred.
  • the substituents R preferably include short chain alkyl groups of not more than 6, more preferably not more than 4 or 3, even more preferably not more than 2, carbon atoms or phenyl as the aryl group. Shorter chain residues are preferred because longer chain residues, a high degree of saturation, and a greater number of substituents can adversely affect the flame retardancy. Particularly effective phosphorus compounds are preferably unsubstituted as possible.
  • substituents R are present, these preferably have a sulfur-containing substituent, such as -SH, -S0 3 NH 4 -SO- or -S0 2 -, or a phosphorus-containing substituents, such as -PO (ONH 4 ) 2 or the like , so as to further improve the flame retardancy.
  • a sulfur-containing substituent such as -SH, -S0 3 NH 4 -SO- or -S0 2 -
  • a phosphorus-containing substituents such as -PO (ONH 4 ) 2 or the like
  • ammonium and phosphonium salts are preferred, as these may also contribute to the flame retardancy.
  • the ammonium and phosphonium ions can instead of hydrogen atoms in each case up to four organic radicals, for. B. above defined substituents R, (ie NR 4 + or PR 4 + ), but in the case of ammonium hydrogen is preferred as a substituent.
  • Examples of such phosphorus compounds of the general formula (II) or (III) are organic phosphorus compounds and salts thereof, such as the monomeric organic phosphorus compounds, including phosphoric acid ester, phosphoric acid amide and phosphonitrile compounds, organic compounds of phosphorous acids, such as esters of phosphorous acid, hypophosphorous acid compounds, phosphines and phosphine oxides such as triphenylphosphine, triphenylphosphine oxide and tricresylphosphine oxide, etc.
  • organic phosphorus compounds and salts thereof such as the monomeric organic phosphorus compounds, including phosphoric acid ester, phosphoric acid amide and phosphonitrile compounds, organic compounds of phosphorous acids, such as esters of phosphorous acid, hypophosphorous acid compounds, phosphines and phosphine oxides such as triphenylphosphine, triphenylphosphine oxide and tricresylphosphine oxide, etc.
  • the flame retardant is an organic phosphorus compound, specifically a 9,10-dihydro-9-oxa-10-phosphaphenanthrene derivative of the general formula (III) or (IIIa) or a salt or ring-opened hydrolyzate thereof
  • X in particular means: substituted or unsubstituted dC 15 alkyl, CC 15 alkenyl, C 3 -C 8 cycloalkyl, C 6 -C 8 aryl, C 7 -C 30 alkylaryl, CC B alkoxy or C 1 -C 6 -alkylthio , or alkali metal, alkaline earth metal, ammonium or phosphorous nium salts thereof, and X is especially selected from -H, -OH, -SH, -ONH 4 , -SNH (Et) 3 , -ONH (Et) 3, -OMelamine, -oguanidine;
  • Yi, Y 2 and Z each independently represent an oxygen atom or a sulfur atom
  • R m each independently represent an alkyl, alkoxy or alkylthio group having 1 to 8 carbon atoms or an aryl group, and m each independently represents an integer of 0 to 4.
  • the polymers have good foamability, good mechanical stability and no disturbing odor properties.
  • the radical R® is an organic or inorganic cation, in particular a salt of a quaternary ammonium compound NR + or a quaternary phosphonium compound PR 4 + , since these may also contribute to the flame retardancy.
  • the ammonium and phosphonium compounds may each have up to four organic radicals instead of hydrogen atoms (ie NR 4 ® or PR 4 ® ).
  • radical R ® in the general formula (Ib) or (Ic) is NH 4 ® and thus the phosphorus compound is the 10-hydroxy-9, 10-dihydro-9-oxa 10-phosphaphenanthrene-10-oxide ammonium salt is:
  • radical R® in the general formula (Ib) or (Ic) is guanidinium and thus the phosphorus compound is the 10-hydroxy-9, 10-dihydro-9-oxa-10-phosphaphenanthrene- 10-oxide guanidinium salt is:
  • DOPO-OMel These compounds have, on their own or as a mixture of several or in a flame retardant composition, very good flame retardant properties. With these flame retardants polymers and polymer foams with improved flame retardancy and improved properties could be created. In addition, even comparatively lower amounts - which do not interfere with foaming - are sufficient in order to achieve the same effect. In particular, these compounds have no interfering softening properties. Surprisingly, it has been found that such flame-retardant polymers and polymer foams have an unexpectedly improved mechanical stability, e.g. with the compound DOPO. In addition, no disturbing odors occur during processing.
  • preferred flame retardants can be selected from the list of claim 11.
  • the expandable polymers of the invention are preferably expandable styrene polymers (EPS) or expandable styrene polymer granules (EPS), in particular of homopolymers and copolymers of styrene, preferably glass clear polystyrene (GPPS), impact polystyrene (HIPS), anionically polymerized polystyrene or impact polystyrene (A-IPS), styrene-alpha-methylstyrene copolymers, acrylonitrile-butadiene-styrene polymers (ABS), Styrene-acrylonitrile (SAN) acrylonitrile-styrene-acrylic ester (ASA), methacrylate-butadiene-styrene (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) - polymers or mixtures thereof or with polyphenylene ether (PPE).
  • this flame retardant system is suitable for thermoplastic polymers, such as cellulose acetate butyrate (CAB) or cellulose acetate butyrate-containing mixtures, as well as for expandable polymers consisting of polylactic acid (PLA) or polylactic acid (PLA).
  • thermoplastic polymers such as cellulose acetate butyrate (CAB) or cellulose acetate butyrate-containing mixtures
  • PLA polylactic acid
  • PLA polylactic acid
  • thermoplastic polymers such as polyamides (PA), polyolefins such as polypropylene (PP) or polyethylene (PE), polyacrylates such as polymethyl methacrylate (PMMA).
  • PA polyamides
  • PP polypropylene
  • PE polyethylene
  • PMMA polyacrylates
  • PC Polycarbonate
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PES polyethersulfones
  • PES polyether ketones or polyether sulfides
  • mixtures in the above amounts ranges with z.
  • rubbers such as polyacrylates or polydienes
  • z As styrene-butadiene block copolymers, biodegradable aliphatic or aliphatic / aromatic copolyesters or thermoplastic polymers such as cellulose acetate butyrate or thermoplastic polyurethane possible.
  • Suitable compatibilizers are e.g. Maleic anhydride-modified styrene copolymers, polymers containing epoxy groups or organosilanes.
  • the effectiveness of the phosphorus compounds can be further improved by the addition of further suitable flame retardant synergists, such as the thermal radical formers dicumyl peroxide, di-tert-butyl peroxide or dicumyl.
  • flame retardants such as melamine, Melamincyanu- rates, metal oxides, metal hydroxides, phosphates, phosphinates or synergists such as Sb 2 0 3 or Zn compounds, can be used.
  • halogen-reduced foams can be used by the Use of the phosphorus compounds and the addition of lesser amounts of halogen-containing, in particular brominated flame retardants, such as hexabromocyclododecane (HBCD), preferably in amounts in the range of 0.05 to 1, in particular 0.1 to 0.5% by weight, produced ,
  • brominated flame retardants such as hexabromocyclododecane (HBCD)
  • the above-mentioned flame-retardant, expandable polymers can be prepared by admixing a flame retardant and melaminium thiosulphate in a manner known per se.
  • An advantageous method procedure envisages that the flame retardant and melamine thiosulphate and a blowing agent are mixed with a polymer melt, for example a styrene polymer melt, with the aid of a dynamic or static mixer and then granulated.
  • a polymer melt for example a styrene polymer melt
  • the flame retardant, as well as melamine thiosulfate are added by means of a dynamic or static mixer to the polymer and melted and the melt is then mixed with propellant and granulated.
  • the flame retardant and melamine thiosulphate by means of a mixer to still granular expandable polymer, e.g. Polystyrene (EPS), mixed and then the mixture is melted and granulated.
  • EPS Polystyrene
  • granule production by suspension polymerization of the monomer, e.g. of styrene, in aqueous suspension in the presence of the flame retardant and melamine thiosulfate and a propellant may be further contemplated that granule production by suspension polymerization of the monomer, e.g. of styrene, in aqueous suspension in the presence of the flame retardant and melamine thiosulfate and a propellant.
  • a further process according to the invention for the preparation of the flame-retardant expandable styrene polymers (EPS) according to the invention comprises the steps:
  • coating agents e.g. Silicates, metal salts of fatty acids, fatty acid esters, fatty acid amides.
  • halogen-free flame-retardant expandable polymers according to the invention such as styrene polymers (EPS) and styrene polymer extrusion foams (XPS) can be prepared by mixing a blowing agent, a flame retardant and melamine thiosulfate in the polymer melt and subsequent extrusion into foam plates, foam strands, or expandable granules.
  • EPS styrene polymers
  • XPS styrene polymer extrusion foams
  • the expandable styrene polymer has a molecular weight> 120,000, more preferably in the range of 180,000 to 220,000 g / mol. Due to the reduction in molecular weight due to shearing and / or the effect of temperature, the molecular weight of the expandable polystyrene is generally about 10,000 g / mol below the molecular weight of the polystyrene used.
  • thermoplastic polymers in particular styrene polymers and expandable styrene polymers (EPS)
  • EPS expandable styrene polymers
  • blowing agents in homogeneous distribution are added to the polymer melt in a proportion of 2 to 10% by weight, preferably 3 to 7% by weight, based on the polymer melt.
  • Suitable blowing agents are the physical blowing agents usually used in expandable polystyrene (EPS), such as aliphatic hydrocarbons having 2 to 7 carbon atoms, alcohols, ketones, ethers or halogenated hydrocarbons. Preference is given to using isobutane, n-butane, isopentane, n-pentane. For XPS, preference is given to using CO 2 or mixtures with alcohols or ketones.
  • the added amount of blowing agent is chosen so that the expandable polymers, in particular styrene polymers (EPS) have an expansion capacity of 7 to 200 g / l, preferably 10 to 50 g / l.
  • EPS styrene polymers
  • the expandable styrene polymer pellets (EPS) according to the invention generally have a bulk density of at most 700 g / l, preferably in the range from 590 to 660 g / l.
  • the styrenic polymer melt may contain additives, nucleating agents, fillers, plasticizers, soluble and insoluble inorganic and / or organic dyes and Pigments, for example IR absorbers, such as carbon black, graphite, petroleum coke, anthracite or aluminum powder, are added together or spatially separated, for example via mixers or side extruders.
  • IR absorbers such as carbon black, graphite, petroleum coke, anthracite or aluminum powder
  • the dyes and pigments are added in amounts ranging from 0.01 to 30, preferably in the range of 1 to 10 wt .-%, added.
  • a dispersing assistant for example organosilanes, polymers containing epoxy groups or maleic anhydride-grafted styrene polymers.
  • Preferred plasticizers are mineral oils, phthalates, which can be used in amounts of from 0.05 to 10% by weight, based on the styrene polymer.
  • a further aspect of the invention relates to a polymer foam, in particular a styrene polymer particle foam or an extruded polystyrene rigid foam (XPS) containing melaminium thiosulfate (bis (2,4,6-triamine-1, 3,5-triazinium) thiosulfate) as Flammtiksynergisten Component of a flame retardant composition or in combination with at least one known flame retardant, in particular with at least one advantageous phosphorus compounds.
  • XPS extruded polystyrene rigid foam
  • An advantageous polymer foam is obtainable from the inventive flame-retardant expandable polymers, in particular from expandable styrene polymers (EPS), in particular by foaming and sintering of the polymer beads or by extrusion of the granules.
  • EPS expandable styrene polymers
  • the halogen-free, flame-retardant polymer foams preferably have one
  • melamine thiosulfate bis (2,4,6-triamine-1, 3,5-triazinium) thiosulfate
  • Flammschutzsynergist as part of a flame retardant composition or in combination with at least one flame retardant, in particular with at least one of the above-mentioned advantageous phosphorus compounds in expandable polymers, in particular in expandable styrene polymers (EPS) or expandable styrene polymer granules (EPS) or in polymer foams, in particular in styrene polymer particle foams obtainable by foaming from expandable polymers, or in extruded polystyrene rigid foams (XPS) used.
  • EPS expandable styrene polymers
  • EPS expandable styrene polymer granules
  • polymer foams in particular in styrene polymer particle foams obtainable by foaming from expandable polymers, or in extruded polystyrene rigid
  • the flame retardants, melaminium thiosulfate and a blowing agent are mixed with a styrene polymer melt by means of a dynamic or static mixer and subsequently foamed or the phosphorus compounds and the melamine thiosulphate are added by means of a dynamic or static mixer to still granular polystyrene polymer and melted, and then added to the melt with blowing agent and foamed.
  • XPS flame-retardant extruded polystyrene rigid foam
  • the preparation of some of the phosphorus compounds mentioned initially results, for example, from AT 508.507, AT 508.304 or WO 2011/000018 A1.
  • the phenylphosphonate salts are prepared according to WO 2011/003773, the oligophosphorus compounds or oligophosphines according to WO 201 1/029901.
  • Thermometer 302.6 g of powdery 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) were suspended in 327.6 g of water, heated to 90 ° C and within 6 h at a Temperature of 90-99 ° C with 190.5 g of 30% hydrogen peroxide. The suspension was then cooled to room temperature, the precipitate was filtered off and washed with water. The drying of the filter residue took place at 150.degree. The crude yield was 312.2 g [96.1% d. Th.]. After recrystallization from acetic acid, the following data were determined:
  • Thermometer, 232, 1 g of 9,10-dihydro-10-hydroxy-9-oxa-10-phosphaphenanthren-10-oxide (DOPO-OH) were suspended in 216.0 g of water and at 71 ° C. with 71.5 g 25% ammonia added. Subsequently, the suspension was heated to 98 ° C and then cooled to room temperature. The entire contents of the flask were emptied onto a drying cup and dried at 120 ° C. The yield was 248.4 g [99.7% d. Th.] Of a white, crystalline solid.
  • the synergists used in the comparative examples were elemental sulfur, Vultac TB7®, a p-butylphenol disulfide polymer (Arkema), elaminium thiosulfate (bis [(2,4,6-triamino-1, 3,5-triazinium) thiosulfate, MelTS). (manufactured by Krems Chemie Chemical Services AG) and ammonium thiosulfate ((NH 4 ) 2 S 2 O 3 ; ATS, Sigma Aldrich).
  • Example 1 (Embodiment - MelTS 10.0% + DOPO-ONKi 5.0%):
  • the polymer melt thus contained was conveyed through a nozzle plate at a rate of 20 kg / h and granulated with a pressurized underwater granulator to give compact EPS granules.
  • Example 2 (Embodiment - MelTS 6.5% + DOPO-ONKi 3.0%): Example 1 was repeated with the difference that 6.5% by weight of melamine thiosulfate and 3.0% by weight of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide ammonium salt (DOPO-O-NH4) , based on the resulting EPS granules, were added.
  • Example 3 (Comparative Example - DOPO-ONH4 15.0%):
  • Example 1 was repeated with the difference that only 15.0% by weight of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthren-10-oxide ammonium salt (DOPO-O-NH 4 ), based on the obtained EPS granules, were added.
  • DOPO-O-NH 4 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthren-10-oxide ammonium salt
  • Example 1 was repeated with the difference that only 9.5% by weight of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide ammonium salt (DOPO-O-NH4), based on the resulting EPS Granules, were added.
  • DOPO-O-NH4 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide ammonium salt
  • Example 1 was repeated with the difference that only 15.0% by weight of melamine thiosulfate (MelTS), based on the resulting EPS granules, were added.
  • MelTS melamine thiosulfate
  • Example 6 (Example - MelTS 10.0% POPP 5.0%):
  • Example 1 was repeated with the difference that 10.0% by weight of melamine thiosulfate and 5.0% by weight of 9,10-dihydro-9-oxa-10-phospha-phenanthrene-10-oxide (DOPO), based on the resulting EPS Granules, were added.
  • DOPO 9,10-dihydro-9-oxa-10-phospha-phenanthrene-10-oxide
  • Example 7 (Comparative Example - DOPO 15.0%):
  • Example 1 was repeated with the difference that only 15.0% by weight of 9,10-dihydro-9-oxa-10-phospha-phenanthrene-10-oxide (DOPO), based on the resulting EPS granules, were added.
  • DOPO 9,10-dihydro-9-oxa-10-phospha-phenanthrene-10-oxide
  • Example 8 (Example - MelTS 10.0% + DOPO-ONH4 5.0% + graphite 4.0%):
  • Example 1 was repeated with the difference that an additional 4% by weight of microcrystalline natural graphite (UF 2 - from Grafit Kropfmühl) was added in the feed zone of the extruder.
  • Example 9 (Example - MelTS 6.5.0% + DOPO-ONH4 3.0% + graphite 4.0%): Example 2 was repeated with the difference that in addition 4 wt% microcrystalline natural graphite (UF2 -. Grafit Kropfmühl) in Feeding area of the extruder were added.
  • Example 10 (Comparative Example - POPO-O-NH4 15.0% + graphite 4.0%):
  • Example 3 was repeated with the difference that an additional 4% by weight of microcrystalline natural graphite (UF 2 - from Grafit Kropfmühl) was added in the feed zone of the extruder.
  • Example 1 (Comparative Example - DOPO-O-NH4 9.5% + graphite 4.0%):
  • Example 4 was repeated with the difference that an additional 4% by weight of microcrystalline natural graphite (UF 2 - from Grafit Kropfmühl) was added in the feed zone of the extruder.
  • Example 12 (comparative example - MelTS 15.0% + graphite 4.0%):
  • Example 5 was repeated with the difference that in addition 4% by weight of microcrystalline natural graphite (UF 2 - from Grafit Kropfmühl) were added in the feed zone of the extruder.
  • Example 13 (Example - MelTS 10.0% POPP 5.0% + graphite 4.0%):
  • Example 6 was repeated with the difference that an additional 4% by weight of microcrystalline natural graphite (UF 2 - from Grafit Kropfmühl) was added in the feed zone of the extruder.
  • Example 14 (Comparative Example -POPP 15.0% + graphite 4.0%):
  • Example 7 was repeated with the difference that in addition 4% by weight of microcrystalline natural graphite (UF 2 - from Grafit Kropfmühl) were added in the feed zone of the extruder.
  • Example 15 (Comparative Example - HBCP 2.5%):
  • Example 1 was repeated with the difference that 2.5% by weight Hexabromcyclodode- can (HBCP - FR 1207 Fa. ICL-IP), based on the resulting EPS granules, were added.
  • Example 16 (Comparative Example - HBCP 2.5% + graphite 4.0%):
  • Example 14 was repeated with the difference that in addition 4% by weight of macrocrystalline natural graphite (UF 2 - from Grafit Kropfmühl), based on the resulting EPS granules, were added.
  • Example 17 (Exemplary Example PS / CAB-MelTS 10.0% + DOPO-O-NF 5.0% + Graphite 4.0%):
  • CAB 500-5 Fa. Eastman cellulose acetate butyrate
  • the polymer melt thus contained was gassed with 3% pentane isomer mixture (80% n-pentane, 20% iso-pentane) and conveyed through a nozzle plate at a rate of 20 kg / h and granulated with a pressurized underwater granulator to form compact foamable granules.
  • Example 18 (Exemplary Example PS / CAB Melts 10.0% + ⁇ - ⁇ - ⁇ ⁇ 5.0% + graphite 4.0%):
  • Example 17 was repeated with the difference that in addition 4% by weight of macrocrystalline natural graphite (UF 2 - from Grafit Kropfmühl), based on the resulting EPS granules, were added.
  • Example 19 (Comparative Example PS / CAB - HBCD 2.5% + graphite 4.0%):
  • HSCD - FR 1207 Fa. ICL-IP hexabromocyclododecane
  • UFS - Grafit Kropfmühl macrocrystalline natural graphite
  • the polymer melt thus contained was conveyed through a die plate with 3% pentane isomer mixture (80% n-pentane, 20% iso-pentane) at a throughput of 20 kg / h and granulated with a pressurized underwater granulator to form compact foamable granules.
  • Table 1 shows the results clearly arranged next to each other, whereby the fire behavior of defined test specimens, the stability or the time to collapse of the foamed foam beads and the odor were checked.
  • Table 1 Testing of the polymers or the polymer foams according to the invention Fire test stability odor
  • Example 11 Comparative Example 4 1 1 ⁇
  • the EPS granules or EPS / CAB granules obtained from the examples were prefoamed with saturated water vapor to form foam beads having a density of 15 to 25 kg / m 3, stored for 24 hours and shaped into foam plates in a molding machine.
  • Test specimens with a thickness of 2 cm were cut from the foam boards, which after 72 hours were subjected to conditioning at 70 ° C. in a fire test in accordance with DIN 4102-2 (B2 small burner test).
  • HBCD hexabromocyclododecane
  • the EPS granules or CAB / EPS granules obtained from the examples were prefoamed with saturated steam to form foam beads having a density of 15 to 25 kg / m 3 , stored for 24 hours and molded in a molded part into foam sheets.
  • Test specimens with a thickness of 2 cm were cut from the foam boards and subjected to a sensory odor test by several laboratory employees.
  • the rating was subjectively according to the criteria "imperceptible” according to the rating 1 to "unpleasant disturbing” with the rating 5.
  • Examples 1, 2, 6, 8, 9 and 13 show the effectiveness of the synergist melamine thiosulphate in polystyrene foams in combination with phosphorus-based flame retardants based on the comparative examples 3, 4, 7, 10, 11 and 14, in which same or higher concentrations showed worse results in the flame retardant properties.
  • Examples 5 and 12 show that melamine thiosulfate alone does not have a sufficient flame retardant effect and acts as a synergist only in combination with flame retardants, in particular with phosphorus-based flame retardants.
  • Examples 15 and 16 are mixed with the flame retardant hexabromocyclododecane (HBCD), which represents the state of the art in polystyrene rigid foams.
  • HBCD flame retardant hexabromocyclododecane
  • Examples 8 to 14 are repetitions of Examples 1 to 7 with the additional equipment with the usual for gray EPS infrared opacifier graphite.
  • Examples 17 to 19 are based on a polymer which consists of 50% cellulose acetate butyrate and 50% polystyrene.
  • Examples 17 and 18 demonstrate the effectiveness of the synergy of melamine thiosulphate and phosphorus based flame retardants in foams based on this polymer matrix.
  • Example 19 serves as a comparative example to 17 and 18 in the system cellulose / tat polystyrene.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fireproofing Substances (AREA)

Abstract

L'invention concerne des polymères expansibles à retard de flamme. Selon l'invention, du thiosulfate de mélaminium (thiosulfate de bis(2,4,6-triamine-1,3,5-triazinium)) est contenu comme agent de synergie de retard de flamme en tant que constituant d'une composition de retard de flamme ou en combinaison avec au moins un agent de retard de flamme.
EP12720389.1A 2011-04-18 2012-04-17 Polymères expansibles à retard de flamme Withdrawn EP2699634A1 (fr)

Applications Claiming Priority (2)

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AT5452011A AT511090B1 (de) 2011-04-18 2011-04-18 Flammgeschützte expandierbare polymerisate
PCT/AT2012/000103 WO2012142634A1 (fr) 2011-04-18 2012-04-17 Polymères expansibles à retard de flamme

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JP2012531504A (ja) * 2009-07-03 2012-12-10 サンパー クンストシュトフ ゲゼルシャフト ミット ベシュレンクテル ハフツング 難燃性発泡性ポリマー
DE102013006937A1 (de) * 2013-04-23 2014-10-23 Zylum Beteiligungsgesellschaft Mbh & Co. Patente Ii Kg Verbesserte Zusammensetzung und deren Verwendung als Flammschutzmittel
CN105732715A (zh) * 2016-01-27 2016-07-06 厦门大学 一种含磷含氟协同阻燃化合物及其制备方法
BR112022005585A2 (pt) * 2019-11-26 2022-06-21 Basf Se Composição de modelagem termoplástica, método de produção de fibras, folhas e moldes e fibra, folha ou molde
CN113105506A (zh) * 2021-05-12 2021-07-13 贵州民族大学 一种磷杂菲衍生物阻燃剂及其制备方法
CN113831442B (zh) * 2021-09-24 2023-07-07 湖南兆恒材料科技有限公司 一种高性价比的阻燃聚甲基丙烯酰亚胺泡沫及其制备方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9325575D0 (en) * 1993-12-14 1994-02-16 Dow Benelux Flame retardant styrenic polymer compositions
DE4436281A1 (de) * 1994-10-11 1996-04-18 Chemie Linz Deutschland Flammfeste, glasfaserverstärkte Polyamidharzmasse mit Melamin- oder Melem-Phosphorsäure-Umsetzungsprodukten als Flammhemmer
US5811470A (en) 1996-05-06 1998-09-22 Albemarle Corporation Flame retardant styrenic polymers
DE102004044380A1 (de) 2004-09-10 2006-03-30 Basf Ag Halogenfreie, flammgeschützte Polymerschaumstoffe
US8101678B2 (en) * 2007-04-03 2012-01-24 Basf Se DOPO flame retardant compositions
JP2012531504A (ja) * 2009-07-03 2012-12-10 サンパー クンストシュトフ ゲゼルシャフト ミット ベシュレンクテル ハフツング 難燃性発泡性ポリマー
US20120108712A1 (en) 2009-07-06 2012-05-03 Basf Se Phenylphosphonate flame retardant compositions
CN102482445A (zh) 2009-09-14 2012-05-30 巴斯夫欧洲公司 含有至少一种低聚磷化合物的不含卤素的阻燃聚合物泡沫
AT508304A1 (de) * 2009-09-24 2010-12-15 Sunpor Kunststoff Gmbh Flammgeschützte expandierbare polymerisate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2012142634A1 *

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