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    • 专利摘要:
    The invention relates to flame-retardant, expandable polymers and polymer foam and their use. According to the invention, it is provided that at least one of the following phosphorus compounds is present as flame retardant:
    公开号:AT511395A1
    申请号:T549/2011
    申请日:2011-04-18
    公开日:2012-11-15
    发明作者:
    申请人:Sunpor Kunststoff Gmbh；
    IPC主号:
    专利说明:

    Flame-retardant expandable polymers
    The present invention relates to flame-retardant, at least one blowing agent-containing, expandable polymers in which at least one phosphorus compound is contained as a flame retardant.
    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.
    STATE OF THE ART
    The equipment of polymer foams with flame retardants is important for many areas. The regulations governing the use of expandable polystyrene (EPS) or expanded polystyrene (XPS) expanded polystyrene foam as building insulation generally require flame retardant equipment. Polystyrene homopolymers and copolymers are predominantly rendered flame-retardant with halogen-containing, in particular brominated organic compounds such as hexabromocyclododecane (HBCD). However, these and a number of other brominated substances have come into discussion or have already been banned because of their potential environmental and health hazards.
    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.
    Partly for this reason, halogen-free flame retardants that 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. In the production of expandable polystyrene by suspension polymerization, the high flame retardant can also reduce the stability of the suspension and thus interfere with the production process or affect.
    The effect of the flame retardants used in polymer polymers in the case of compact polymers is frequently due to the peculiarities of such mixtures. * "* · ·
    Foams and the different fire behavior or because of different fire tests unpredictable.
    WO 2006/027241 describes a halogen-free flame retardant for polymer foams which does not significantly affect the foaming process and also enables the production of predominantly closed-cell polymer foams. This flame retardant is a known and used since the early 1970s phosphorus compound, for example, according to JP-A 2004-035495, JP-A 2002-069313 or JP-A 2001-115047 is to produce. Most preferably, but not exclusively, the phosphorus compound is 9,10-dihydro-9-oxa-10-phospha-phenanthrene-10-oxide (6H-dibenz [c, e] -oxaphosphorine-6-oxide, DOP-O, CAS [35948-25-5]) mentions:
    DOPO
    This flame retardant is already well used, but there is a need to make such polymers or polymer foams even more resistant to fire and to increase this with the lowest possible content of flame retardants or without the content of flame retardants. Furthermore, DOPO has a softening effect in polymers, especially in styrene polymers, so that, with sufficient flame-retardant action, the mechanical stability requirements demanded of construction products in most European countries can no longer be achieved. This is a major disadvantage of DOPO, which eliminates the use of DOPO in foamed polymers.
    In AT 508.304 it is described that the concentration of DOPO and thus the softening effect can be reduced to such an extent by adding sulfur and / or at least one sulfur-containing compound or sulfur compound that polymer foams which meet the minimum requirements for foamability and mechanical stability , can be made. The softening effect could not be completely eliminated, but only reduced.
    • ·
    In AT 508.507 9,10-dihydro-9-oxa-10-phosphaphenanthren-10-thione or -10-sulfide (DOPS) and some derivatives thereof are described. An unpleasant side effect, especially of sulfur, but also of many sulfur compounds, however, is that z.b. can result in processing odorous compounds.
    It is therefore the object of the present invention to provide a flame-resistant, flame-retardant, expandable polymer with a low content of good resistance to fire
    Flame retardants and good quality, in particular good foamability and good mechanical stability, and not to create disturbing odor properties.
    Furthermore, it is an object of the invention to provide an advantageous process for the preparation of such polymers.
    A further object of the invention is to provide a halogen-free flame-retardant, but qualitatively corresponding, polymer foam with advantageous fire behavior and good mechanical properties as well as an advantageous production method therefor.
    It is particularly desirable that the polymer or polymer foam also meet the stringent fire resistance requirements for e.g. Construction applications met, such as the B2 small burner test according to DIN 4102-2 or the small burner test according to EN 11925-2.
    DISCLOSURE OF THE INVENTION
    This object is achieved for the polymer of the type mentioned by the characterizing features of claim 1. According to the invention, it is provided that at least one of the following phosphorus compounds is present as flame retardant: Phosphorus compound according to formula (Ia):
    (*) * * * * * * * * * * * * * «*» * * 4 * * * »·· * ft · 4» «I f ··» · I «« 4 * - * * * »I **» 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-OH) - or salts thereof according to formula (Ib):
    (Ib) (DOPO-OR) - or their ring-opened hydrolysates according to formula (Ic): | 0 " '' - ρ-οβφ ^ i
    Ohoh (Ic).
    With these phosphorus compounds, it is possible to achieve high-quality, highly fire-resistant polymers meeting the standards even at low levels of flame retardants. The polymers have good foamability, good mechanical stability and no disturbing odor properties.
    Advantageous developments of these polymers are described by the features of the dependent claims:
    Thus, for example, it is possible that the radical R® is an organic or inorganic cation, in particular a salt of a quaternary ammonium compound NR4 + or a quaternary phosphonium PR4 as these may also contribute to the flame retardancy. The ammonium and phosphonium compounds may each have up to four organic radicals (i.e., NR4® and PR4®, respectively) instead of hydrogen atoms. ft · »« * «· · * * ft * ft *« * ft ft · «··« »« * · · · «« * a · «ft« ·· ** ·
    In this context, it has been found to be particularly advantageous if the radical R® in the general formula (Ib) or (Ic) NH4® and thus the phosphorus compound, the 10-hydroxy-9,1Q-dihydro-9-oxa-10 phosphaphenanthrene 10-oxide ammonium salt is:
    nh4 DOPO-ONH4
    Furthermore, it has been found to be particularly advantageous if the radical R® in the general formula (Ib) or (Ic) is guanidium and thus the phosphorus compound is the 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene- 10-oxide guanidinium salt is: O p'C I 0 0 NH, Λ θ 0 · Λ-NH, / * NH, DOPO-OGua
    Furthermore, it has been found to be particularly advantageous if the radical R® in the general formula (Ib) or (Ic) is melamine and thus the phosphorus compound is the 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene- 10-oxide melamine salt is: .. .. NH, "P: " * λ ...
    O € NH '' 'V NH, DOPO-OMel (f ··· «♦ η * * * ι ι» · «*** *
    As shown in the later embodiments, these new compounds, alone or as a mixture of several or in one
    Flame retardant composition included, very good flame retardancy. With these flame retardants polymers and polymer foams with improved flame retardancy and improved properties could be created. In addition, comparatively lower amounts - which do not disturb the foaming - are sufficient 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.
    Advantageously, it is provided that the / the phosphorus compound (s) in an amount of 0.5 to 25 wt .-%, in particular 1 to 15 wt .-%, based on the total weight of the polymer or the granules thus obtained, is included /are.
    To increase the flame retardant effect, it is advantageous to use synergists which alone have little or no flame retardant effect, but in combination with the mentioned phosphorus compounds show a surprising increase in the flame retardant effect.
    Sulfur and / or sulfur compounds or sulfur compounds have proved to be particularly advantageous as synergists, in particular in an amount of from 1 to 25% by weight, in particular from 2 to 15% by weight, based on the total weight of the polymer.
    As sulfur compounds, for example, sulfides, sulfites, sulfates, sultans, sulfoxylates, sulfones, sulfonates, thiosulfates, thionites, thionates, disulfates, sulfoxides, sulfur nitrides, sulfur halides and / or organosulfur compounds such as thiols, thioethers, thiophenes, etc. are advantageously used.
    Furthermore, sulfur compounds have proved to be advantageous in the analysis by means of thermogravimetry (TGA) according to EN ISO 11358 below 115 ° C, a weight loss of less than 10 wt .-%, for example, ammonium thiosulfate, Dicaprolactamdisulfid, Zinksuifid, polyphenylene sulfide, etc.
    It is particularly advantageous if the sulfur-containing compound or sulfur compound has at least one S-S bond, at least one of the sulfur atoms being in divalent form, e.g. Disulfites, dithionites, cystine, amylphenol disulfide, poly-tert-butylphenol disulfide, etc., »* • · *»
    Surprisingly, it has been found that thiosulphate compounds, such as melamine thiosulphate (MetTS)
    Nit NH. N._./ 'S n NΗ ς - ( ^ NΗ © θO - S - 0 © © NH' ) - NH.
    M- ^ N NH, NR, (MelTS) and the para-tertiobutylphenol disulfide polymer oh Γ
    para-Tertiobutylphenoldisulfid polymer are particularly effective.
    Also surprising is the beneficial low odor of the synergists melamine thiosulfate and para-Tertiobutylphenoldisulfid polymer. In addition, by using these synergistic sulfur compounds, the total amount of flame retardant can be reduced, resulting in a variety of benefits, i.a. in the production process, in the cost, the mechanical properties of the product, etc., leads. Above all, the foaming process and the mechanical properties of the foam are only insignificantly influenced, resulting in a high-quality product.
    The expandable polymers according to the invention are preferably expandable styrene polymers (EPS) or expandable styrene polymer granules (EPS) which are in particular 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 esters (ASA), methyl acrylate-butadiene-styrene (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) polymers or mixtures thereof or with
    Polyphenylene ether (PPE) exist. Especially for polystyrene, the need for high-quality products is particularly high.
    Furthermore, this flame retardant system is suitable for thermoplastic polymers, such as cellulose acetate butyrate (CAB), as well as for expandable polymers consisting of polylactic acid (PLA) or polylactic acid (PLA).
    Said styrene polymers may be used to improve the mechanical properties or the temperature resistance optionally using compatibilizers with 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), polyethersulfones (PES), polyether ketones or polyether sulfides (PES) or mixtures thereof, generally in proportions of not more than 30 wt .-%, preferably in the range of 1 to 10 wt .-%, based on the polymer melt, mixed.
    Furthermore, mixtures in the above amounts ranges with z. B hydrophobically modified or functionalized polymers or oligomers, 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 suitable flame retardant synergists, such as the thermal radical formers dicumyl peroxide, di-tert-butyl peroxide or dicumyl.
    In addition, additional flame retardants, such as melamine,
    Melamine cyanurates, metal oxides, metal hydroxides, phosphates, phosphinates or
    Synergists such as Sb203 or Zn compounds are used.
    If the complete absence of halogens of the polymer or of the polymer foam can be dispensed with, halogen-reduced foams can be produced by the use of the phosphorus compounds and the addition of lesser amounts of halogen-containing, in particular brominated flame retardants, such as
    Hexabromcyclododecane (HBCD), preferably in amounts ranging from 0.05 to 1, in particular 0.1 to 0.5 wt .-%, are prepared.
    Another aspect of the invention relates to the preparation of such polymers. According to the invention, the above-mentioned flame-retardant, expandable polymers can be prepared by admixing the above flame retardants and optionally sulfur and / or at least one sulfur-containing compound or sulfur (compound as synergists in a conventional manner.
    An advantageous procedure provides that the flame retardant, for example DOPO-OH or DOPO-ONH4, the sulfur compound, for example melamine thiosulfate or para-Tertiobutylphenoldisulfid polymer, and a blowing agent with a polymer melt, e.g. a styrene polymer melt, mixed by means of a dynamic or static mixer and then granulated.
    Alternatively, it can be provided that the flame retardant, for example DOPO-OH or DOPO-ONH4, and the sulfur compound, for example melaminium thiosulfate or para-Tertiobutylphenoldisulfid polymer are added by means of a dynamic or static mixer to the polymer and melted and then the melt with propellant is added and granulated.
    Alternatively it can further be provided that the flame retardant, for example DOPO-OH or DOPO-ONH, and the sulfur compound, for example melamine thiosulphate or para-tert-butylphenol disulphide, by means of a dynamic or static mixer to still granular expandable polymer, e.g. Polystyrene (EPS), mixed and then the mixture is melted and granulated.
    Alternatively, it can further be provided that the granule preparation by suspension polymerization of the monomers. e.g. of styrene, in aqueous suspension in the presence of the flame retardant, for example DOPO-OH or DOPO-ONH4, and the sulfur compound, for example melamine thiosulfate or para-tert-butylphenol disulfide polymer, 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:
    Dosing together in an extruder of PS or EPS granules with a
    Molecular weight of Mw > 120,000 g / mol, preferably from 150,000 to 250,000 g / mol, more preferably from 180,000 to 220,000 g / mol, and of the formula (2) * * * Μ * * * ι * * # * * *:: Ιο ;: ::: *: * tt «· * · ♦ * * * * * * ** *******
    Flame retardants, for example DOPO-OH or DOPO-0 - NH4 > and the sulfur compound, for example melamine thiosulphate or para-tertiobutylphenol disulphide, and if appropriate of one or more further additives, melting all components together in the extruder - optional metered addition of at least one blowing agent
    - Mix all components at a temperature > 120 ° C
    Granulation by means of pressurized underwater granulation, e.g. 1-20 bar, to a granule size < 5 mm, preferably 0.2 to 2.5 mm, at a water temperature of 30 to 100 ° C, in particular 50 to 80 ° C, optionally superficial coating with coating agents, e.g. Silicates, metal salts of fatty acids, fatty acid esters, fatty acid amides.
    The 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 in a blowing agent, a phosphorus compound of the general formulas (Ia) and / or the hydrolysis product (Ic) and / or a salt (Ic) thereof, and of elemental sulfur and / or a sulfur-containing compound or sulfur compound in the polymer melt and subsequent extrusion to foam sheets, foam strands, or expandable granules are prepared.
    Preferably, the expandable styrenic 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 by shear and / or temperature, the molecular weight of the expandable polystyrene is generally about 10,000 g / mol below the molecular weight of the polystyrene used.
    The styrene polymer melt may also be blended with polymer recyclates of said thermoplastic polymers, in particular styrene polymers and expandable styrene polymers (EPS) in amounts which do not substantially impair their properties, generally in amounts of at most 50% by weight, in particular in amounts of from 1 to 20 wt .-%.
    As a rule, one or more 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 commonly used in expandable polystyrene (EPS), such as aliphatic hydrocarbons having 2 to 7 carbon atoms, alcohols, ketones, ethers or halogenated hydrocarbons. Iso-butane, n-butane is preferred.
    iso-pentane, n-pentane used. 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.
    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.
    Further, the styrenic polymer melt may contain additives, nucleating agents, fillers, plasticizers, soluble and insoluble inorganic and / or organic dyes and pigments, e.g. IR absorbers, such as carbon black, graphite, petroleum coke, anthracite or aluminum powder, together or spatially separated, e.g. via mixers or side extruders. In general, the dyes and pigments are added in amounts ranging from 0.01 to 30, preferably in the range of 1 to 10 wt .-%, added. For homogeneous and microdispersed distribution of the pigments in the styrene polymer, it may be expedient in particular for polar pigments to use a dispersing aid, 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 as flame retardant at least one phosphorus compound of the general formula (Ia) and / or their ring-opened hydrolyzates or salts thereof.
    To improve the effect optionally elemental sulfur and / or at least one sulfur-containing compound or sulfur compound may be included as Flammschutzsynergist.
    A particularly 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.
    The halogen-free, flameproofed polymer foams preferably have a density in the range from 8 to 200 g / l, more preferably in the range from 10 to 50 g / l and are preferably more than 80%, particularly preferably 95 to 100%, closed-line or closed-cell have a predominantly closed-cell structure with more than 0.5 cells per mm3. »* · * * T * - *
    According to the invention, at least one of the phosphorus compounds of the general formulas (Ia) or (Ib) and their ring-opened hydrolyzates according to (Ic) as flame retardants, optionally in combination with sulfur and / or a sulfur-containing compound or sulfur compound as Flammschutzsynergist, 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 foams (XPS).
    For the production of flame-retardant extruded polystyrene rigid foam (XPS), the phosphorus compounds, the sulfur compounds and a blowing agent are mixed with a styrene polymer melt by means of a dynamic or static mixer and then foamed or the phosphorus compounds and the sulfur compounds are added by means of a dynamic or static mixer still granular polystyrene polymer added and melted, and then added to the melt with blowing agent and foamed.
    Preparation of the Phosphoric Compounds or Synergists: 1. Preparation of 9,10-dihydro-10-hydroxy-9-oxa-10-phosphaphenanthren-10-one or -1-Q-oxide (DOPO-OH) a) Preparation of DOPO -OH in an aqueous medium:
    In a multi-necked flask equipped with a stirrer, reflux condenser and thermometer, 302.6 g of powdery 9,10-dihydro-9-oxa-10-phosphaphenan-10-thene-10-oxide (DOPO) was suspended in 327.6 g of water Heated to 90 ° C and treated 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:
    Mp 203 ° C (ref .: 203-204 ° C, J. Cadogan, supra)
    Elemental Analysis C12H9O3P (M: 232.17 g / mol): calc. C: 62.08%; H: 3.91%; P: 13.34% gef. C: 61.5%; H: 4.2%; P: 13.2% b) Preparation of DOPO-OH in alcoholic-aqueous medium:
    In a multi-necked flask equipped with a stirrer, reflux condenser and thermometer, 302.6 g of DOPO were pre-dissolved in 200.0 g of methanol at 25 ° C. and heated continuously to 80 ° C. over 6 h with 317.5 g of 30%. added hydrogen peroxide. The resulting suspension was cooled to room temperature, the precipitate was filtered off and washed with methanol. The drying of the filter residue took place at 150.degree. The crude yield was 277.1 g [85.3% d. Th.]. After recrystallization from acetic acid, the following data were determined: mp: 203 ° C (lit: 203 - 204 ° C); Phosphorus content: gef. 13.3%, over 13.34%. c) Preparation of DOPO-OH in an aromatic-aqueous medium:
    In a multi-necked flask equipped with a stirrer, reflux condenser and thermometer, 302.6 g of DOPO were dissolved in 150.0 g of toluene at 70 ° C and with continuously rising to 85 DC temperature within 7 h with 204.1 g 30% Hydrogen peroxide added. Subsequently, 183.7 g of toluene-water mixture were distilled off. The residue was cooled to room temperature and filtered. Drying of the filter residue was carried out at 150 ° C. The crude yield was 314.9 g [96.9% d, Th.]. After recrystallization from acetic acid, the following data were determined:
    Mp: 202-203 ° C (lit. 203-204 ° C); Phosphorus content: gef. 13.2%, over 13.34%. 2. Preparation of 9,10-dihydro-10-hydroxy-9-oxa-10-phosphaphenanthrene-10-one or 10-oxide ammonium salt (DOPQ-ONH4) a) Liquid Process:
    In a multi-necked flask equipped with a stirrer, reflux condenser and thermometer, 232.1 g of 9,10-dihydro-10-hydroxy-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-OH) in 216.0 g of water suspended and mixed at 25 ° C with 71.5 g of 25% ammonia. 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.
    Mp .: 234-240 ° C (decomp.)
    Elemental Analysis Ci2H12N03P (M: 249.20 g / mol): calc. C: 57.83%; H: 4.85%; N: 5.62%; P: 12.43% gef. C: 57.5%; H: 5.1%; N: 5.5%; P: 12.4% b) Solid state method: × 232.0 g of dry and ground DOPO-OH having a grain fineness < 45 pm were placed in a closed grinding chamber and while the shearing work slowly with 78.3 g of ammonia, 25% in water. At the end of the ammonia addition, the millbase had heated to 77 ° C, without losing the powdery state of matter. After a 5-minute mixing time, the shearing unit was stale and the ground material allowed to rest for 1 h. Thereafter, the mixture was reground again for 5 min and then emptied onto a drying cup, distributed and dried at 140 ° C. The yield was 242 g [97.2% d. Th.] Of a white, crystalline solid, the data of which substantially corresponded to those of Example 1. 3. Preparation of 9,10-dihydro-10-hydroxy-9-oxa-10-phosphaphenanthrene-10-one or 10-oxide melamine salt (DOPO-OMeh
    In a multi-necked flask equipped with a stirrer, reflux condenser and thermometer, 92.8 g of DOPO-OH were suspended in 400 g of water and mixed at 50 ° C. with 50.4 g of melamine. Subsequently, the suspension was heated to 90 ° C and held for 4 h at this temperature. Thereafter, it was cooled to room temperature. The precipitate was filtered off and washed with water. The drying was carried out at 160 ° C, and the yield was 141.4 g [98.7% d. Th.] Of a white, crystalline solid.
    Mp .: 246-250 ° C (decomp.)
    Elemental analysis C15H15N603P (M: 358.29 g / mol): calc. C: 50.28%; H: 4.22%; N: 23.46%; P: 8.64% gef. C: 49.8%; H: 4.5%; N: 23.3%; P: 8.5% 4, Preparation of 9,10-dihydro-10-hydroxy-9-oxa-10-phosphaphenanthrene-10-one and 10-oxide quanidinium salt (DOPO-OGua)
    In a multi-necked flask equipped with a stirrer, reflux condenser and thermometer, a mixture of 100.0 g of water, 100 g of ethanol and 36.0 g of guanidinium carbonate was prepared and heated to 75 ° C. Subsequently, 92.8 g of DOPO-OH were added in portions over a period of 5.5 h. After C02 development was no longer detectable, the reaction mass was thickened destiffativ. The remaining crude crystal pulp (135.6 g) was applied to a drying cup and dried at 110 ° C. The yield was 100.5 g [86.0% d. Th.] Of a white, crystalline solid.
    Mp: 278-280 ° C (decomp.) 9 9 5 5
    Elemental Analysis Ci3H14N303P (Μ: 291.24 g / mol): calc. C: 53.61%; H: 4.84%; N: 14.42%; P: 10.63% gef. C: 53.3%; H: 5.1%; N: 14.3%; P: 10.5% 5. Preparation of Melaminium Thiosulfate (MelTS) a) In a multi-necked flask equipped with stirrer, reflux condenser and thermometer, 1218.7 g of distilled water containing 147.8 g of conc. Hydrochloric acid (37%) and 189.1 g melamine mixed. The suspension was heated to reflux temperature. After a clear solution, the flask contents were cooled to 96 ° C and 348.6 g of a 34% sodium thiosulfate solution. A precipitation reaction occurred. The precipitate was cooled with stirring to room temperature, filtered off and washed thoroughly with distilled water. The drying of the filter residue took place at 110.degree. The yield was 265.1 g [96.5% d. Th] of a white, crystalline solid.
    Mp .: 178-180 ° C (Zers.)
    Elemental Analysis C6H14N1203S2 (M: 366.38 g / mol): calc. C: 19.67%; H: 3.85%; N: 45.88%; O: 13.10%; S: 17.50% gef. C: 19.8%; H: 4.0%; N: 45.6%; O: 13.5%; S: 17.2% b) In a multi-necked flask equipped with stirrer, reflux condenser and thermometer, 1200.0 g of distilled water were added to 252.2 g of melamine and 158.1 g of sodium thiosulfate. The suspension was heated to 95 ° C. Subsequently, at a metering rate of 0.9 g / min, 197.1 g of conc. Hydrochloric acid (37%) was added dropwise, then the reaction mass was cooled to room temperature with stirring, the precipitate was filtered off and washed with distilled water. The filter cake was again taken up in 1100 g of distilled water, stirred vigorously and filtered off. The drying of the filter residue took place at 110.degree. The yield was 356.8 g [97.4% d. Th.] Of a white, crystalline solid, the data of which substantially corresponded to those of Example 1. c) In a multi-necked flask equipped with stirrer, reflux condenser and thermometer, 1130 g of distilled water, 252.2 g of melamine and 158.1 g of sodium thiosulfate were mixed and heated to 90 ° C. Within 1.5 hours, 174.2 g of 37.5% strength phosphoric acid were added dropwise to the initially charged suspension at 90-93 ° C. Thereafter, the precipitate was cooled while the agitator was running to room temperature and filtered through a Blauband filter. The filter cake was washed with water and then dried at 110 ° C. The yield was 328.5 g [89% d. Th.] Of a white, crystalline solid, the data of which substantially corresponded to those of Example 1.
    As synergists in the comparative examples were elemental sulfur, Vultac TB7®, a pt-butylphenol disulfide polymer (Arkema), melaminium thiosulfate (bis [(2,4,6-tri-amino-1,3,5-triazinium) thiosulfate, MelTS). (manufactured by Krems Chemie Chemical Services AG) and ammonium thiosulfate ((NH4) 2S203; ATS, Sigma Aldrich).
    These examples enable the person skilled in the art to prepare or obtain the desired flame retardants as such, any desired starting materials and the synergists.
    Production of Expandable Polymers or Polmer Foams:
    The preparation of flame-retardant expandable polymers, e.g. of EPS, in the form of granules or beads is known per se to those skilled in the art. The preparation of the polymers according to the invention with the above flame retardants and optionally sulfur compounds works essentially analogously. For example, the embodiments of WO 2006/027241, AT 508.304 or AT 508.507 can be used. The same applies to the polymer foams or XPS.
    EXAMPLES
    The invention will be described below by way of example by way of concrete, but not limiting, exemplary embodiments described in detail and nacharbeitbar. Subsequently, these examples are then also used to demonstrate the effectiveness.
    The present invention will be described hereinbelow in detail with reference to 19 concrete embodiments 1 to 4, 7 to 12, 15 to 19, 21 and 22, and 24 and 25. Examples 5, 6, 13 and 14 are comparative examples. Examples 20 and 23 are reference examples of the currently used in the production of flame-retardant styrene polymer foams (EPS and XPS) flame retardant HBCD. # * * »Ll · Μ 4 ·· · I · ·» · # -f-7 ···· ♦ ··· «W · · · · · · · · * «« »* B * · ***« * - ·
    Example 1 (Embodiment - DQPQ-OH 15%):
    A styrene polymer (SUNPOR EPS-STD: 6 wt% pentane, chain length MW = 200,000 g / mol, nonuniformity MW / Mn = 2.5) was in the catchment area of a
    Twin screw extruder 15% by weight of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-OH) based on the resulting EPS granules, admixed and melted in the extruder at 19CTC. 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 form compact EPS granules.
    Example 2 (Embodiment - DOPO-ONH ^ 15%):
    Example 1 was repeated with the difference that 15% by weight of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthren-10-oxide ammonium salt (DOPO-ONH4), based on the resulting EPS granules, were added ,
    Example 3 (Embodiment - DQPS-OGua 15%):
    Example 1 was repeated with the difference that 15% by weight of preparation of 9,10-dihydro-10-hydroxy-9-oxa-10-phosphaphenanthren-10-one or 10-oxide guanidiniumsalz (DOPO OGua) related were added to the resulting EPS granules.
    Example 4 (Embodiment - DOPO-OMel 15%):
    Example 1 was repeated with the difference that 15% by weight of 9,10-dihydro-10-hydroxy-9-oxa-10-phosphaphenanthren-10-one and 10-oxide melaminiumsalz (DOPO-OMel), based on the obtained EPS granules, were added.
    Example 5 (Comparative Example -MelTS 15%):
    Example 1 was repeated with the difference that 15% by weight of melamine thiosulphate (MelTS), based on the resulting EPS granules, were metered in (but no phosphorus compound).
    Example 6 (Comparative Example - Vultac TB7 15%):
    Example 1 was repeated with the difference that 15% by weight of para-Tertiobutylphenoldisulfid polymer (Vultac TB7 from. Arkema), based on the resulting EPS granules, were added (but no phosphorus compound).
    Example 7 (Embodiment - DOPO-ONHi 5.0% + MelTS 10.0%):
    Example 1 was repeated with the difference that 5% by weight of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthren-10-oxide ammonium salt (DOPO-ONH4) and 10% by weight of melamine thiosulfate (MelTS), based on the obtained EPS granules were added.
    Example 8 (Embodiment - DOPO-OGua 5.0% + MelTS 10.0%):
    Example 1 was repeated with the difference that 5% by weight of 9,10-dihydro-10-hydroxy-9-oxa-10-phosphaphenanthren-10-one and 10-oxide-guanidiniumsalz (DOPO-OGua) and 10 wt% melamine thiosulfate (MelTS), based on the resulting EPS granules were added.
    Example 9 (Example - DOPQ-OMel 5.0% + MelTS 10.0%):
    Example 1 was repeated with the difference that 5% by weight of 9,10-dihydro-10-hydroxy-9-oxa-10-phosphaphenanthren-10-one or 10-oxide melaminium salt (DOPO-OMel) and 10% by weight of melamine thiosulfate (MelTS), based on the resulting EPS granules were added.
    Example 10 (Embodiment - DOPO-ONH4 5.0% + Vultac TB7 10.0%):
    Example 1 was repeated with the difference that 5% by weight of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide ammonium salt (DOPO-ONH4) and 10% by weight of para-tertiobutylphenol disulfide polymer (Vultac TB7 ), based on the resulting EPS granules were added.
    Example 11 (Embodiment - DOPQ-OH 5.0% + Vultac TB7 10.0%):
    Example 1 was repeated with the difference that 5% by weight of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-OH) and 10% by weight of para-tertiobutylphenol disulfide polymer (Vultac TB7), based on the resulting EPS granules were added.
    Example 12 (Embodiment - DOPO-ONH, 5.0% + ATS 10.0%);
    Example 1 was repeated with the difference that 5% by weight of 10-hydroxy-9,10-dihydro-9-oxa-1Q-phosphaphenanthrene-10-oxide ammonium salt (DOPO-ONH4) and 10% by weight of ammonium thiosulfate (ATS - Sigma Aldrich) , based on the EPS granules obtained, were added.
    Example 13 (Comparative Example - DOPS-OH 5.0% + MelTS 10.0%):
    Example 1 was repeated with the difference that 5% by weight of 9,10-dihydro-10-hydroxy-9-oxa-10-phosphaphenanthrene-10-thione or -10-sulphide (DOPS-OH) and 10% by weight of melamine thiosulphate {MelTS ), based on the resulting EPS granules were added.
    Example 14 (Comparative Example - POPO 5.0% + Vuitac TB7 10.0%):
    Example 1 was repeated with the difference that 5 wt% of 9,10-dihydro-9-oxa-10-phospha-phenanthrene-10-oxide (DOPO) and 10 wt% para-tertiobutylphenol disulfide polymer (Vuitac TB7), based on the obtained EPS granules were added.
    Example 15 (Embodiment - DOPO-ONH4 3.0% + MelTS 6.5%):
    Example 1 was repeated with the difference that 3% by weight of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthren-10-oxide ammonium salt (DOPO-ONH4) and 6.5% by weight of melamine thiosulfate (MelTS), based on the resulting EPS granules were added.
    Example 16 (Embodiment - DOPO-ONHd 3.0% + Vuitac TB7 6.5%):
    Example 1 was repeated with the difference that 3% by weight of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide ammonium salt (DOPO-ONH4) and 6.5% by weight of para-tertiobutylphenol disulfide polymer (Vuitac TB7 ), based on the resulting EPS granules were added.
    Example 17 (embodiment - DOPO-OH 3.0% + Vuitac TB7 6.5%):
    Example 1 was repeated with the difference that 3% by weight of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-OH) and 6.5% by weight of para-tertiobutylphenol disulfide polymer (Vuitac TB7), based on the resulting EPS granules were added.
    Example 18 (Embodiment - DOPO-ONH4 3.0% + ATS 6.5%):
    Example 1 was repeated with the difference that 3% by weight of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide ammonium salt (DOPO-ONH4) and 6.5% by weight of ammonium thiosulfate (ATS-Sigma Aldrich) , based on the EPS granules obtained, were added.
    Example 19 (Embodiment - DOPO-ONH41.0% + MelTS 2.2%):
    Example 1 was repeated with the difference that 1% by weight of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide ammonium salt (DOPO-ONH4) and 2.2% by weight of melamine thiosulphate (MelTS), based on the resulting EPS granules were added.
    Example 20 (Reference Example - HBCD 2.5%):
    Example 1 was repeated with the difference that 2.5% by weight hexabromocyclododecane (HBCD - FR 1207 Fa. ICL-IP), based on the resulting EPS granules, were added.
    Example 21 (Example - DQPO-ONH4 5.0% + MelTS 10.0% + graphite 4.0%): Example 7 was repeated with the difference that in addition 4 wt% macrocrystalline natural graphite (UF2 -. Grafit Kropfmühl), based on the obtained EPS granules were added.
    Example 22 (Example - DOPO-ONH4 3.0% + MelTS 6.5% + graphite 4.0%): Example 15 was repeated with the difference that additionally 4% by weight of macrocrystalline natural graphite (UF2 - from Grafit Kropfmühl), based on the resulting EPS granules were added.
    Example 23 (reference example - HBCD 2.5% + graphite 4.0%):
    Example 20 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 24 (Exemplary embodiment PS / CAB-DQPQ-QNKt 5.0% + MelTS 10.0% + graphite 4.0%):
    A 50:50 mixture of styrene polymer (SUNPOR EPS-STD: 6% by weight of pentane,
    Chain length MW = 200,000 g / mol, nonuniformity MW / Mn = 2.5) and
    Cellulose acetate butyrate (CAB 500-5 from Eastman) in the feed area of a twin-screw extruder 5.0% by weight of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthren-10-oxide ammonium salt (DOPO-ONH4), 10 wt .% Melaminiumthiosulfat (MelTS) and 4 wt% macrocrystalline natural graphite (UF2 -. Grafit Kropfmühl), based on the resulting polymer mixture, mixed and melted in the extruder at 190 ° C. The polymer melt thus obtained 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 25 (comparative example PS / CAB - HBCO 2.5% + graphite 4.0%):
    A 50:50 mixture of styrene polymer (SUNPOR EPS-STD: 6 wt% pentane, chain length MW = 200,000 g / mol, nonuniformity MW / Mn = 2.5) and
    Cellulose acetate butyrate (CAB 500-5 from Eastman) were in the catchment area of a twin-screw extruder 2.5% by weight hexabromocyclododecane (HBCD - FR 1207 Fa. ICL-IP) and 4 wt% macrocrystalline natural graphite (UF2 -. Grafit Kropfmüh!), Based on the resulting polymer mixture, mixed and melted in the extruder at 190 ° C. 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.
    The following Table 1 shows the results clearly arranged side by side, whereby the fire behavior of defined test specimens, the stability or the time until collapse of the foamed foam beads and the odor were checked.
    TABLE 1 Examination of the polymers according to the invention or polymer foams
    Fire Test Stability Odor Example 1 Embodiment 3 1 1 Example 2 Embodiment 3 1 1 Example 3 Embodiment 4 1 1 Example 5 Comparative Example 5 1 1 Example 6 Comparative Example 5 1 2 Example 7 Embodiment 1 1 1 Example 8 Embodiment 2 1 ._ 1._ Example 9 Embodiment 2 1 _1 Example 10 Embodiment 1 1 2 Example 11 Embodiment 1 1 2 Example 12 Embodiment 2 1 3 Example 13 Comparative Example 3 1 3 Example 14 Comparative Example 3 3 2 Example 15 Embodiment 2 1 1 Example 16 Embodiment 2 1 2 Example 17 Embodiment 2 1 2 Example 18 Embodiment 3 1 3 Example 19 Embodiment 4 1 1 Example 20 Reference Example 1 1 i | Example 21 Embodiment 1 1 1 Example 22 Embodiment 2 1 1 Example 23 Reference Example 1 1 1 Example 24 Embodiment 3 1 2 Example 25 Embodiment 3 1 2
    The results of the experiments in the three right columns were obtained by tests with products of Examples 1 to 25 described above. in detail:
    Fire test (column 3 in Table 1):
    The EPS granules or EPS / CAB granules obtained from the examples were prefoamed with saturated steam to form foam beads having a density of 15 to 25 kg / m 3, temporarily 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).
    The results scored with numbers between 1 and 5 were evaluated relative to hexabromocyclododecane (HBCD) flame retarded EPS (Reference Examples 20 and 23). Values of 1 in the column "Fire test" mean that the test substance behaves as well as HBCD-protected EPS with regard to its fire behavior. Values of 5 mean that the fire behavior is very poor and corresponds to non-flame-retardant EPS.
    Stability of the foam structures (column 4 in Table 1):
    The EPS granules or EPS / CAB granules obtained from the examples were exposed to saturated water vapor and the time until collapse of the beads occurred determined. This time was evaluated in the summary of results relative to EPS particles without flame retardants. Only Example 14 showed a softening effect. All other phosphorus-based flame retardants showed equal stability (no collapse until the end of pre-expansion).
    Where " stability " Values of 1 indicate that the beads have normal stability. Values of 5 mean that the beads immediately collapse without creating a foam structure that would be suitable for molding.
    Odor (column 5 in Table 1):
    The EPS granules or EPS / CAB granules obtained from the examples were prefoamed with saturated steam to form foam beads having a density of 15 to 25 kg / m 3, temporarily 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 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.
    Evaluation and discussion of the results (Table 1):
    Examples 1 to 4 show the basic activity of DOPO-OH and the salts DOPO-ONH4, DOPO-Omel and DOPO-OGua as flame retardants.
    Examples 5 and 6 show that MelTS and Vultac TB7 alone show no flame retardant effect at the same levels.
    Examples 1 and 2 are the reference examples of the effectiveness of the sulfur-containing synergists (Examples 7 to 12 and 15 to 18), since the same and lower total concentrations of flame retardant and synergist equal and usually even better results in the flame retardant effect could be achieved.
    Examples 1 to 4, 7 to 12, 15 to 19 and 21 and 22 are examples of expandable polymers according to the invention with a flame retardant according to formula (Ia), (Jb) or (Ic).
    In Examples 1 to 23 EPS was used as raw material, in Examples 24 and 25 a mixture of polystyrene and cellulose acetate butyrate.
    Example 20 or 23 applies as further reference for the prior art. All the evaluations of the tests refer to these reference tests by denoting the results with numerical values from 1 to 5, whereby small numbers, in particular 1, tend to be more advantageous, larger Numbers, in particular 5, are more disadvantageous.
    In none of the examples, with the exception of Example 14 (DOPO), was the mechanical stability of the prefoamed granules or of the foamed bodies produced therefrom significantly affected.
    The moldings made with Vultac TB7 were found to have a mild phenolic odor. On the moldings prepared from Examples 12 and 18, a pungent odor was perceptible. On the moldings of Comparative Example 13 (DOPS-OH) sulfur compounds (H2S-like smell) were clearly noticeable.
    The moldings from Examples 24 and 25 had the typical odor of cellulose acetate butyrate, which is also detectable on the raw material.
    权利要求:
    Claims (23)
    [1]
    1. Flame-retardant, at least one blowing agent-containing, expandable polymers, characterized in that as flame retardants at least one of the following phosphorus compounds is contained: - phosphorus compound according to formula (la): • * r * · t_. • tili , 0 PC i OH. ^ 0

    u da) 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthren-10-oxide (DOPO-OH) - or salts thereof according to formula (Ib): (Ib) (DOPO-OR) - or their ring-opened hydrolysates according to formula (Ic):

    Q Ρ-ΟΘΘρ OH OH

    (Ic) -
    [2]
    2. Expandable polymers according to claim 1, characterized in that the radical R® is an organic or inorganic cation.
    [3]
    3. Expandable polymers according to one of the preceding claims, characterized in that the radical R® is a salt of a quaternary ammonium compound NR4 + or a quaternary phosphonium PR4 +.
    [4]
    4. Expandable polymers according to one of the preceding claims, characterized in that the radical R® in the general formula (Ib) or (Ic) NH4® and the phosphorus compound 10-hydroxy-9,10-dihydro-S-oxa-l0 -phosphaphenanthren-1Q-oxide ammonium salt:

    4 ® NH.

    dopo-onh4
    [5]
    5. Expandable polymers according to one of the preceding claims, characterized in that the radical R® in the general formula (Ib) or (Ic) is guanidinium and the phosphorus compound is 10-hydroxy-9,10-dihydro-9-oxa-10 phospha-10-oxide guanidinium:

    DOPOOGua
    [6]
    6. Expandable polymers according to one of the preceding claims, characterized in that the radical R © in the general forms! (Ib) or (Ic) is melamine and the phosphorus compound is 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide melaminium salt:

    DOPO OMEL
    [7]
    7. Expandable polymers according to one of the preceding claims, characterized in that the / the phosphorus compound (s) in an amount of 0.5 to 25% by weight, in particular 1 to 15 wt .-%, based on the total weight of the polymer , is / are included.
    [8]
    8. Expandable polymers according to one of the preceding claims, characterized in that the expandable polymers are expandable styrene polymers (EPS) or expandable styrene polymer granules (EPS), which in particular of homo- and copolymers of styrene, preferably glass clear polystyrene (GPPS), impact polystyrene (HIPS), anionically polymerized polystyrene or toughened polystyrene (A-IPS), styrene-alpha-methylstyrene copolymers, acrylonitrile-butadiene-styrene polymers (ABS), styrene-acrylonitrile (SAN) acrylonitrile-styrene-acrylic ester (ASA), methyacrylate-butadiene -Styrol (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) polymers or mixtures thereof or with polyphenylene ether (PPE) and / or that the expandable polymers consist of cellulose acetate burtyrate (CAB) or contain cellulose acetate burtyrate (CAB) and / or the expandable polymers consist of polylactic acid (PLA) or contain polylactic acid (PLA).
    [9]
    9. Expandable polymers according to one of the preceding claims, characterized in that the expandable polymers are mixtures of styrene polymers according to claim 8 with expandable thermoplastic polymers such as cellulose acetate burtyrate (CAB), thermoplastic polyurethane (TPU), polylactic acid, etc., wherein the thermoplastic polymers to 1 to 99 wt .-%, based on the total polymer composition, are included.
    [10]
    10. Expandable polymers according to one of the preceding claims, characterized in that additionally contained as flame retardant synergist sulfur and / or at least one sulfur-containing compound or sulfur compound.
    [11]
    11. Expandable polymers according to one of the preceding claims, characterized in that sulfur and / or the at least one sulfur-containing compound or sulfur compound in an amount of 1 to 25 wt.%, In particular 2 to 15 wt%, based on the total weight of the polymer , is included.
    [12]
    12. Expandable polymers according to one of the preceding claims, characterized in that the sulfur-containing compound or sulfur compound has at least one S-S bond, wherein at least one of the sulfur atoms is present in divalent form, for example ammonium thiosulfate.
    [13]
    13. Expandable polymers according to one of the preceding claims, characterized in that the sulfur-containing compounds or sulfur compounds in an analysis by means of thermogravimetry below 115 ° C, a weight loss of less than 10 wt .-% have.
    [14]
    14. Expandable polymers according to one of the preceding claims, characterized in that the flame retardant synergist melamine thiosulfate or bis [(2,4,6-tri-amino-1,3,5-triazinium) thiosulfate is:

    (Melts)
    [15]
    15. Expandable polymers according to one of the preceding claims, characterized in that the flame retardant synergist para-Tertiobutylphenoldisulfid polymer is: • * * * * ft το • • • JÖ *



    Γ |
    [16]
    16. A process for the preparation of flame-retardant, expandable polymers according to one of the preceding claims, characterized in that at least one phosphorus compound of the general formulas (la), (Ib) or (Ic) is used according to one of claims 1 to 7 as flame retardants, and optionally as an additional flame retardant or -Synergist sulfur and / or at least one sulfur-containing compound or sulfur compound according to any one of claims 10 to 15.
    [17]
    17. A process for the preparation of flame-retardant expandable polymers, in particular styrene polymers (EPS), according to claim 16, wherein the flame retardant, melaminium thiosulfate and a blowing agent with a polymer melt, in particular a Styrolpolymerschmelze, mixed with the aid of a dynamic or static mixer and then granulated or wherein the flame retardant and melaminium thiosulfate, by means of a dynamic or static mixer to granular polymer, in particular polystyrene polymer, are mixed and melted, and the melt is then mixed with propellant and granulated or - wherein the flame retardant and melamine thiosulfate by means of a mixer to granular polymer , in particular polystyrene polymer, are admixed, and the mixture is then melted and granulated or wherein the granule preparation by suspension polymerization, esp of styrene, in aqueous suspension in the presence of the flame retardant, of melamine thiosulfate and a propellant.
    [18]
    18. Process for the preparation of flame-retardant expandable styrene polymers (EPS) according to claim 16 or 17 comprising the steps of: dosing together in an extruder of PS or EPS granules having a molecular weight of Mw > 120 000 g / mol, preferably from 150 000 to 250 000 g / mol, particularly preferably from 180 000 to 220 000 g / mol, and of the flame retardant, the flame retardant synergist and optionally one or more further additives, in particular a) further flame retardant synergists , eg thermal radical generators, such as dicumyl peroxide, in a concentration of 0.1 to 20% by weight, b) infrared opacifiers, e.g. Graphite, carbon black, petroleum coke, anthracite, aluminum, titanium dioxide, in a concentration of 0.1 to 10% by weight, c) stabilizers, e.g. Nitroxyl radical-forming substances such as HTEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl) in a concentration of 0.1 to 1% by weight, d) further halogenated or halogen-free flame retardants, e.g. HBCD, DOP-O, magnesium hydroxide, in a concentration of 0.1 to 20% by weight and / or e) fillers, e.g. Chalk, talc, silicates, in a concentration of 1 to 20 wt% common melting of all components in the extruder, optional metered addition of at least one blowing agent, mixing of all components at a temperature > 120 ° C, granulation by means of pressurized underwater granulation, at e.g. 1-20 bar, to a granule size < 5 mm, preferably 0.2 to 2.5 mm, at a water temperature of 30 to 100 ° C, in particular 50 to 80 ° C, optionally superficial coating with coating agents, e.g. Silicates, metal salts of fatty acids, fatty acid esters, fatty acid amides.
    [19]
    19. Flame-retardant, expandable polymers, in particular styrene polymers (EPS), obtainable by a process according to one of claims 16 to 18.
    [20]
    20. Polymer foam, in particular styrene polymer particle foam or extruded polystyrene rigid foam (XPS), containing as flame retardant at least one phosphorus compound of the formulas (Ia), (Ib) or (Ic) according to one of claims 1 to 7, and optionally as an additional flame retardant or -Synergist sulfur and / or at least one sulfur-containing compound or sulfur compound according to any one of claims 10 to 15. :: 3Q:
    [21]
    21. Polymer foam according to claim 20 obtainable from flame-retardant expandable polymers according to one of claims 1 to 15, in particular from expandable styrene polymers (EPS), in particular by foaming and sintering of the polymers or by extrusion.
    [22]
    22. Polymer foam according to claim 20 or 21 having a density between 7 and 200 kg / m3 and / or a predominantly closed cell cell structure with more than 0.5 cells per mm3, in particular with a structure in which more than 80% of the cells are closed-celled ,
    [23]
    23. Use of at least one phosphorus compound of the formula (Ia) and / or salts thereof of the formula (Ib), and / or their ring-opened hydrolyzates of the formula (Ic) according to one of claims 1 to 7, as flameproofing agents, and optionally of sulfur and / or at least one sulfur-containing compound or sulfur compound according to any one of claims 10 to 15 as a flame retardant synergist, in expandable polymers, especially in expandable styrene polymers (EPS) or expandable styrene polymer granules (EPS) or in polymer foams, in particular in styrene polymer particle foams available by foaming from expandable polymers, or in extruded polystyrene rigid foams (XPS). Vienna, April 18, 2011
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    ATA549/2011A|AT511395B1|2011-04-18|2011-04-18|FLAME-PROOF EXPANDABLE POLYMERISATE|ATA549/2011A| AT511395B1|2011-04-18|2011-04-18|FLAME-PROOF EXPANDABLE POLYMERISATE|
    CN201280019044.8A| CN103608388A|2011-04-18|2012-04-17|Flame-retardant expandable polymers|
    US14/112,913| US20140128489A1|2011-04-18|2012-04-17|Flame-retardant expandable polymers|
    RU2013151091/04A| RU2013151091A|2011-04-18|2012-04-17|FIRE RESISTANT FOAMING POLYMERS|
    KR1020137030430A| KR20140058424A|2011-04-18|2012-04-17|Flame-retardant expandable polymers|
    PCT/AT2012/000104| WO2012142635A2|2011-04-18|2012-04-17|Flame-retardant expandable polymers|
    JP2014505457A| JP2014514409A|2011-04-18|2012-04-17|Flame retardant foam polymer|
    EP12718030.5A| EP2699627A2|2011-04-18|2012-04-17|Flame-retardant expandable polymers|
    US15/243,778| US10035892B2|2011-04-18|2016-08-22|Flame-retardant expandable polymers|
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