WO2011029901A1 - Halogenfreie, flammgeschützte polymerschaumstoffe, enthaltend mindestens eine oligophosphorverbindung - Google Patents
Halogenfreie, flammgeschützte polymerschaumstoffe, enthaltend mindestens eine oligophosphorverbindung Download PDFInfo
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- WO2011029901A1 WO2011029901A1 PCT/EP2010/063304 EP2010063304W WO2011029901A1 WO 2011029901 A1 WO2011029901 A1 WO 2011029901A1 EP 2010063304 W EP2010063304 W EP 2010063304W WO 2011029901 A1 WO2011029901 A1 WO 2011029901A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0038—Use of organic additives containing phosphorus
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/22—After-treatment of expandable particles; Forming foamed products
- C08J9/228—Forming foamed products
- C08J9/232—Forming foamed products by sintering expandable particles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/50—Phosphorus bound to carbon only
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- 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
- C09K21/02—Inorganic materials
- C09K21/04—Inorganic materials containing phosphorus
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
Definitions
- the invention relates to halogen-free, flame-retarded polymer foams which contain at least one cyclic or acyclic oligophosphorus compound as flame retardant, and to processes for their preparation.
- Flame retardant polymer foam finishing is important for a variety of applications, such as expandable polystyrene (EPS) or expanded polystyrene (XPS) expanded polystyrene foam for building insulation.
- EPS expandable polystyrene
- XPS expanded polystyrene
- Flame retardant polymer foam finishing is important for a variety of applications, such as expandable polystyrene (EPS) or expanded polystyrene (XPS) expanded polystyrene foam for building insulation.
- EPS expandable polystyrene
- XPS expanded polystyrene
- No. 6,369,140 describes inter alia cyclic oligophosphines in low concentrations as stabilizers for polyolefins against degradation by heat, mechanical stress or light.
- WO 2009/030708 describes cyclic and polymeric arylphosphines as flame retardants in various plastics, for example polycarbonates or acrylonitrile-butadiene-styrene copolymers (ABS).
- EP-A 834 529 describes expandable styrene polymers containing as halogen-free flame retardant a mixture of a phosphorus compound and a dehydrating metal hydroxide.
- wt .-% Mg (OH) 2 and 5 to 10 wt .-% triphenyl phosphate (TPP) are incorporated in an extruder in molten polystyrene and granulated and the granules in aqueous suspension with blowing agent nachim ceremoniesgniert.
- WO 00/34342 describes a process for the preparation of expandable polystyrene by suspension polymerization of styrene in the presence of 5-50 wt .-% expandable graphite and optionally 2 to 20 wt .-% of a phosphorus compound as a flame retardant.
- DOP 9,10-dihydro-9-oxa-10-phospha-phenanthren-10-oxide
- halogen-free flame retardants must be used to achieve the same flame retardancy of halogen-containing flame retardants usually in significantly higher amounts.
- thermoplastic polymers such as polystyrene
- halogen-free flame retardants that can be used in thermoplastic polymers, such as polystyrene, often not be used in polymer foams, since they either interfere with the foaming process or affect the mechanical and thermal properties of the polymer foam.
- the high levels of flame retardant can reduce the stability of the suspension.
- the effect of the flame retardants used in thermoplastic polymers in polymer foams is often unpredictable due to the different fire behavior and different fire tests.
- the object of the invention was therefore to find a halogen-free flame retardant for polymer foams, in particular for expandable polystyrene (EPS) or polystyrene extrusion foam boards (XPS), which does not significantly affect the foaming process and the mechanical properties and in particular the production of predominantly closed-cell polymer foams allows.
- EPS expandable polystyrene
- XPS polystyrene extrusion foam boards
- the phosphorus content of the oligophosphorus compounds is preferably in the range from 5 to 50% by weight, in particular in the range from 8 to 25% by weight.
- Preferred flame retardants contain at least one cyclic or acylic oligophosphine or oligophosphine halide with 2 to 6 phosphorus atoms and at least one phosphorus-phosphorus bond.
- all phosphorus atoms are linearly or cyclically linked by P-P bonds.
- Suitable oligophosphorus compounds are, for example, those having the structures Ia, Ib or Ic:
- the radicals R'-R 4 can be selected independently of one another from the group of Ci-Ci6-alkyl, Ci-Ci6-alkenyl, Ci-Ci6-alkoxy, Ci-Ci6-alkenyloxy, C3-Cio-cycloalkyl, C3-Cio -Cycloalkoxy, C6-Cio-aryl, C6-Cio-aryloxy, C6-Cio-aryl-Ci-Ci6-alkyl, C6-Cio-aryl-Ci- Cie-alkoxy, NR 2 R 3 , COR 2 , COOR 2 and CONR 2 R 3 , and the radicals X 1 and X 2 independently of one another are O or S.
- oligophosphorus compounds has one of the following structures IIa, IIb or IIc:
- radicals R'-R 5 are independently selected from the group of Ci-Ci6-alkyl, Ci-Ci6-alkenyl, Ci-Ci6-alkoxy, Ci-Ci6-alkenyloxy, C3-Cio-cycloalkyl, C3-Cio -Cycloalkoxy, C6-Cio-aryl, C6-Cio-aryloxy, C6-Cio-aryl-Ci-Ci6-alkyl, C6-Cio-aryl-Ci- Cie-alkoxy, NR 2 R 3 , COR 2 , COOR 2 and CONR 2 R 3 , and the radicals X 1 and X 2 independently of one another are O or S.
- cyclic oligophosphorus compounds of the following structure III are suitable:
- the radicals R 1 are selected from the group of C 1 -C 16 -alkyl, C 1 -C 16 -alkenyl, C 1 -C 16 -alkoxy, C 1 -C 16 -alkenyloxy, C 3 -C 10 -cycloalkyl, C 3 -C 10 -cycloalkoxy, C 6 -C 10 -alkyl.
- aryl, C6-C10-aryloxy, C 6 -C 10 -aryl-Ci-Ci6-alkyl, Ce-Cio-aryl-Ci-Cie-alkoxy, NR 2 R 3 , COR 2 , COOR 2 and CONR 2 R 3 and n an integer between 2 and 6 means
- Particularly preferred flame retardants are tetraphenyldiphosphine monoxide, tetraphenyldiphosphine monosulfide, tetraphenyldiphosphine dioxide, tetraphenyldiphosphine disulfide, tetraphenyldiphosphine oxide sulfide, pentaphenylpentaphospholane, 1,1,3,3-tetramethoxy-2-phenyltriphosphine-1,3-dioxide, 1,1,3,3-tetraethoxy-2 - phenyltriphosphine-1, 3-dioxide, 1, 1, 3, 3-tetraallyloxy-2-phenyltriphosphine-1, 3-dioxide or mixtures thereof are used.
- the halogen-free, flame-retarded polymer foams according to the invention generally contain the cyclic or acyclic oligophosphorus compounds in an amount in the range from 0.5 to 25% by weight, based on the polymer foam. Quantities of 5-15% by weight, based on the polymer foam, ensure sufficient flame retardancy, in particular in the case of foams made from expandable polystyrene.
- the effectiveness of the oligophosphorus 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 this case, 0.05 to 5 parts by weight of the flame retardant synergists are usually used in addition to the oligophosphorus compound.
- flame retardants such as melamine, melamine cyanurates, metal oxides, metal hydroxides, phosphates, phosphinates, expandable graphite or synergists such as Sb 2 0 3 or Zn compounds may additionally be used.
- Suitable additional halogen-free flame retardants are commercially available under the names Exolit OP 930, Exolit OP 1312, DOPO, HCA-HQ, M-ester Cyagard RF-1241, Cyagard RF-1243, Fyrol PMP, AlPi, Melapur 200, Melapur MC, APP ,
- halogen-reduced foams can be used in amounts of from 0 by using the oligophosphorus compound according to the invention and by adding lesser amounts of halogen-containing, in particular brominated flame retardants, such as hexabromocyclodecane (HBCD). 05 to 1, in particular 0.1 to 0.5 wt .-% are produced.
- halogen-containing, in particular brominated flame retardants such as hexabromocyclodecane (HBCD).
- the halogen-free, flame-retardant polymer foams preferably have a density in the range from 5 to 200 kg / m 3 , particularly preferably in the range from 10 to 50 kg / m 3 and are preferably more than 80%, more preferably 95 to 100% closed-cell.
- the halogen-free, flame-retarded polymer foams preferably comprise a thermoplastic polymer, in particular a styrene polymer.
- EPS expandable styrene polymers
- XPS styrene polymer extrusion foams
- the expandable styrene polymer preferably has a molecular weight M w in the range from 120,000 to 400,000 g / mol, particularly preferably in the range from 180,000 to 300,000 g / mol, measured by gel permeation chromatography with refractometric detection (RI) in relation to polystyrene standards. 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.
- styrene polymers preference is given to glass-clear polystyrene (GPPS), toughened polystyrene (HIPS), anionically polymerized polystyrene or toughened polystyrene (A-IPS), styrene-a-methstyrene copolymers, acrylonitrile-butadiene-styrene polymers (ABS), styrene polymers.
- GPPS glass-clear polystyrene
- HIPS toughened polystyrene
- A-IPS anionically polymerized polystyrene or toughened polystyrene
- ABS acrylonitrile-butadiene-styrene polymers
- SAN Acrylonitrile
- ASA acrylonitrile-styrene-acrylic ester
- MBS methyl methacrylate-butadiene-styrene
- MABS methyl methacrylate-acrylonitrile-butadiene-styrene
- 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% by weight in total , preferably in the range of 1 to 10 wt .-%, based on the polymer melt, are mixed.
- PA polyamides
- PE polyolefins
- PE polypropylene
- PE polyethylene
- PMMA polymethyl methacrylate
- PC Polycarbonate
- polyesters such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), polyethersulfones (PES), polyether ketones or polyether
- B hydrophobically modified or functionalized polymers or oligomers, rubbers such as polyacrylates or polydienes, z.
- styrene-butadiene block copolymers or biodegradable aliphatic or aliphatic / aromatic copolyesters possible.
- Suitable compatibilizers are, for example, maleic anhydride-modified styrene copolymers, polymers or organosilanes containing epoxide groups.
- the styrene polymer melt may also be mixed with polymer recyclates of the above-mentioned thermoplastic polymers, in particular styrene polymers and expandable styrene polymers (EPS), in amounts which do not substantially impair their properties, generally in amounts of not more than 50% by weight, in particular in amounts of from 1 to 20 wt .-%.
- EPS expandable styrene polymers
- the propellant-containing styrene polymer melt generally contains one or more propellants in a homogeneous distribution in a proportion of 2 to 10 wt .-%, preferably 3 to 7 wt .-%, based on the propellant-containing styrene polymer melt.
- Suitable blowing agents are the physical blowing agents commonly used in EPS, such as aliphatic hydrocarbons having 2 to 7 carbon atoms, alcohols, ketones, ethers or halogenated hydrocarbons. Preference is given to using isobutane, n-butane, isopentane, n-pentane. For XPS, preference is given to using CO 2 or mixtures with alcohols or ketones.
- finely divided internal water droplets can be introduced into the styrene polymer matrix. This can be done for example by the addition of water in the molten styrene polymer matrix. The addition of the water can be done locally before, with or after the propellant dosage. A homogeneous distribution of the water can be achieved by means of dynamic or static mixing. As a rule, from 0 to 2, preferably from 0.05 to 1.5,% by weight of water, based on the styrene polymer, is sufficient.
- Expandable styrene polymers with at least 90% of the internal water in the form of inner water droplets with a diameter in the range of 0.5 to 15 ⁇ m form foams with sufficient cell number and homogeneous foam structure during foaming.
- the added amount of blowing agent and water is chosen so that the expandable styrene polymers (EPS) have an expansion capacity oc, defined as bulk density before foaming / bulk density after foaming at most 125, preferably 25 to 100.
- EPS expandable 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.
- EPS expandable styrene polymer pellets
- additives, nucleating agents, fillers, plasticizers, soluble and insoluble inorganic and / or organic dyes and pigments, for example IR absorbers, such as carbon black, graphite or aluminum powder may be added to the styrene polymer melt together or spatially separated, eg via mixers or side extruders.
- the dyes and pigments are added in amounts ranging from 0.01 to 30, preferably in the range of 1 to 5 wt .-%.
- 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.
- the blowing agent can be mixed into the polymer melt.
- One possible method comprises the stages a) melt production, b) mixing c) cooling d) conveying and e) granulation.
- Each of these stages can be carried out by the apparatuses or apparatus combinations known in plastics processing.
- static or dynamic mixers are suitable, for example extruders.
- the polymer melt can be taken directly from a polymerization reactor or produced directly in the mixing extruder or a separate melt extruder by melting polymer granules.
- the cooling of the melt can be done in the mixing units or in separate coolers.
- pressurized underwater granulation granulation with rotating knives and cooling by spray misting of tempering liquids or sputtering granulation may be considered for the granulation.
- Apparatus arrangements suitable for carrying out the method are, for example: a) polymerization reactor - static mixer / cooler - granulator
- the arrangement may include side extruders for incorporation of additives, e.g. of solids or thermally sensitive additives.
- the propellant-containing styrene polymer melt is usually conveyed through the nozzle plate at a temperature in the range from 140 to 300.degree. C., preferably in the range from 160 to 240.degree. Cooling down to the range of the glass transition temperature is not necessary.
- the nozzle plate is heated at least to the temperature of the blowing agent-containing polystyrene melt.
- the temperature of the nozzle plate is in the range of 20 to 100 ° C above the temperature of the blowing agent-containing polystyrene melt. This prevents polymer deposits in the nozzles and ensures trouble-free granulation.
- the diameter (D) of the nozzle bores at the nozzle exit should be in the range from 0.2 to 1.5 mm, preferably in the range from 0.3 to 1.2 mm, particularly preferably in the range from 0.3 to 0 , 8 mm lie. Thus, even after strand expansion granulate sizes under 2 mm, in particular in the range 0.4 to 1, 4 mm set specifically.
- EPS halogen-free flame-retardant, expandable styrene polymers
- suspension polymerization is preferably used as the monomer styrene alone. However, up to 20% of its weight may be replaced by other ethylenically unsaturated monomers, such as alkylstyrenes, divinylbenzene, acrylonitrile, 1,1-diphenyl ether or ⁇ -methylstyrene.
- the customary auxiliaries for example peroxide initiators, suspension stabilizers, blowing agents, chain transfer agents, expansion aids, nucleating agents and plasticizers, may be added.
- the cyclic or acyclic oligophosphorus compound of the present invention is added in the polymerization in amounts of from 0.5 to 25% by weight, preferably from 5 to 15% by weight.
- Propellants are added in amounts of 3 to 10 wt .-%, based on monomer. It can be added before, during or after the polymerization of the suspension.
- Suitable propellants are aliphatic hydrocarbons having 4 to 6 carbon atoms.
- inorganic Pickering dispersants for example magnesium pyrophosphate or calcium phosphate
- suspension stabilizers In the suspension polymerization arise pearly, substantially round particles with an average diameter in the range of 0.2 to 2 mm.
- the finished expandable styrene polymer granules can be coated by glycerol esters, antistatic agents or anticaking agents.
- the EPS granules may contain glycerol monostearate GMS (typically 0.25%), glyceryl tristearate (typically 0.25%) finely divided silica Aerosil R972 (typically 0.12%) and Zn stearate (typically 0.15%), and antistatic be coated.
- GMS glycerol monostearate
- glyceryl tristearate typically 0.25%
- finely divided silica Aerosil R972 typically 0.12%
- Zn stearate typically 0.15%
- the expandable styrene polymer granules according to the invention can be prefoamed in a first step by means of hot air or water vapor to foam particles having a density in the range of 8 to 200 kg / m 3 , in particular 10 to 50 kg / m 3 and in a second step in a closed mold to be welded to particle moldings.
- the expandable polystyrene particles can be made into polystyrene foams having densities of from 8 to 200 kg / m 3, preferably from 10 to 50 kg / m 3 .
- the expandable particles are prefoamed. This is usually done by heating the particles with water vapor in so-called pre-expanders.
- the pre-expanded particles are then welded into shaped bodies.
- the prefoamed particles are brought into shapes which do not close in a gas-tight manner and are charged with steam. After cooling, the moldings can be removed.
- organic phosphorus compounds FR1 to FR 9 used as flame retardants in the examples were synthesized according to the following preparation instructions:
- Tetraphenyldiphosphine dioxide and tetraphenyldiphosphine disulfide from tetraphenyldiphosphine (after: W. Kuchen, H. Buchwald, Chem. Ber., 1958, 91, 2871-2877.) tetraphenyldiphosphine:
- Phosphine, phosphite and toluene are placed in the flask with stirring. Within 0,5h heated to 1 13 ° C (120 ° C bath temperature). Stirred for 6h at this temperature, with a slight evolution of gas is visible. After that, no gas evolution was seen. 31 P-NMR from the reaction solution shows complete conversion.
- Phenyldichlorophosphine (8.9 g, 0.05 mol) was added with stirring to 1.2 g (0.05 mol) of magnesium turnings in 50 ml of tetrahydrofuran as solvent.
- the reaction was highly exothermic and required a condensation condenser, slow addition of phenyldichlorophosphine and occasional external cooling in a water bath.
- salt began to precipitate. The addition was complete after 30 minutes. After several hours, only traces of metal remained.
- the salt was dissolved by adding a small amount of acetone and magnesium was filtered off. After addition of 30 ml, a two-phase system with an organic layer and a salt water layer was formed. Upon addition of a second portion of water to the organic layer, 4.0 g (84%) of tetraphenylcyclotetraphosphine having a melting point of 148-152 ° C was precipitated.
- the mixture of polystyrene melt, blowing agent and flame retardant was at 60 kg / h through a nozzle plate with 32 holes (diameter of the nozzle 0.75 mm) promoted. With the help of pressurized underwater granulation, compact granules with a narrow size distribution were produced.
- the granules were prefoamed by the action of flowing steam and, after being stored for 12 hours by further treatment with steam, sealed in a closed mold to form foam blocks of a density of 15 kg / m 3 .
- Expandable polystyrene with flame retardants was prepared analogously to Examples 1 to 3:
- the uniformly kneaded in the extruder at 180 ° C gel is passed through a calming zone and extruded after a residence time of 15 minutes with an outlet temperature of 105 ° C through a 300 mm wide and 1, 5 mm wide nozzle into the atmosphere.
- the foam is passed through a mold channel connected to the extruder to form a foamed sheet having a cross section of 650 mm x 50 mm and a density of 35 g / l.
- the product was cut into plates.
- the fire behavior of the samples was tested after a storage time of 30 days according to DIN 4102.
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Abstract
Description
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Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP10751679.1A EP2478044B1 (de) | 2009-09-14 | 2010-09-10 | Halogenfreie, flammgeschützte polymerschaumstoffe, enthaltend mindestens eine oligophosphorverbindung |
CN2010800405898A CN102482445A (zh) | 2009-09-14 | 2010-09-10 | 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 |
PL10751679T PL2478044T3 (pl) | 2009-09-14 | 2010-09-10 | Bezfluorowcowe, ogniochronne polimerowe tworzywa piankowe zawierające co najmniej jeden związek oligofosforowy |
RU2012114679/05A RU2012114679A (ru) | 2009-09-14 | 2010-09-10 | Свободные от галогена, огнестойкие полимерные пенопласты, содержащие, по меньшей мере, одно олигофосфорное соединение |
US13/394,348 US20120178842A1 (en) | 2009-09-14 | 2010-09-10 | Halogen-free, flame-proof polymer foams containing at least one oligophosphorus compound |
BR112012005740A BR112012005740A2 (pt) | 2009-09-14 | 2010-09-10 | espuma de polímero, retardante de chama, livre de halogênio, processo para a produção de polímeros de estireno expansíveis tornados retardantes de chama por um produção de polímeros de estireno expansíveis tornados retardantes de chama por um método livre de halogênio, polímero de estireno expansível tornado retardante de chama por um método livre de halogênio, e, processo para a produção de espumas de poliestireno moldadas retardantes de chama por um método livre de halogênio |
MX2012002896A MX2012002896A (es) | 2009-09-14 | 2010-09-10 | Espumas polimericas a prueba de flama, libres de halogeno, que contienen por lo menos un compuesto oligofosforoso. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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EP09170196.1 | 2009-09-14 | ||
EP09170196 | 2009-09-14 |
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WO2011029901A1 true WO2011029901A1 (de) | 2011-03-17 |
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PCT/EP2010/063304 WO2011029901A1 (de) | 2009-09-14 | 2010-09-10 | Halogenfreie, flammgeschützte polymerschaumstoffe, enthaltend mindestens eine oligophosphorverbindung |
Country Status (9)
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US (1) | US20120178842A1 (de) |
EP (1) | EP2478044B1 (de) |
KR (1) | KR20120083406A (de) |
CN (1) | CN102482445A (de) |
BR (1) | BR112012005740A2 (de) |
MX (1) | MX2012002896A (de) |
PL (1) | PL2478044T3 (de) |
RU (1) | RU2012114679A (de) |
WO (1) | WO2011029901A1 (de) |
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WO2011121001A1 (de) * | 2010-04-01 | 2011-10-06 | Basf Se | Flammschutzmittel |
WO2012142634A1 (de) | 2011-04-18 | 2012-10-26 | Sunpor Kunststoff Gesellschaft M.B.H. | Flammgeschützte expandierbare polymerisate |
WO2012151596A2 (de) | 2011-04-18 | 2012-11-15 | Sunpor Kunststoff Gesellschaft M.B.H. | Expandierbare polymerisate aus celluloseacetatbutyrat und styrolpolymerisat |
US8636929B2 (en) | 2010-05-21 | 2014-01-28 | Basf Se | Nanoporous foamed active compound-containing preparations based on pharmaceutically acceptable thermoplastically workable polymers |
EP2706086A1 (de) | 2012-09-05 | 2014-03-12 | Basf Se | Verfahren zur Herstellung von Schaumstoffplatten niedriger Dichte durch Extrusion von Styrolpolymeren unter Verwendung von Hydrofluorolefinen als Treibmittel |
US9115312B2 (en) | 2010-04-01 | 2015-08-25 | Basf Se | Flame retardant |
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US8759411B2 (en) * | 2010-02-01 | 2014-06-24 | Basf Se | Derivatives of diphosphines as flame retardants for polyurethanes |
US20110196052A1 (en) * | 2010-02-05 | 2011-08-11 | Basf Se | Flame retardants |
EP3087128B1 (de) | 2013-12-27 | 2019-09-11 | Dow Global Technologies LLC | Flammhemmende copolymere von dialkyl(meth)acryloyloxyalkylphosphat- oder dialkyl(meth)acryloyloxyalkylphosphonat-monomeren und daraus hergestellte polymerschaumstoffe |
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EP3227378B1 (de) | 2014-12-05 | 2018-09-05 | SABIC Global Technologies B.V. | Flammhemmende polystyrolzusammensetzung |
CN106589200B (zh) * | 2016-12-24 | 2018-10-02 | 上海普信高分子材料有限公司 | 一种阻燃型聚苯乙烯的制备方法 |
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- 2010-09-10 EP EP10751679.1A patent/EP2478044B1/de not_active Not-in-force
- 2010-09-10 BR BR112012005740A patent/BR112012005740A2/pt not_active IP Right Cessation
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Cited By (6)
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WO2011121001A1 (de) * | 2010-04-01 | 2011-10-06 | Basf Se | Flammschutzmittel |
US9115312B2 (en) | 2010-04-01 | 2015-08-25 | Basf Se | Flame retardant |
US8636929B2 (en) | 2010-05-21 | 2014-01-28 | Basf Se | Nanoporous foamed active compound-containing preparations based on pharmaceutically acceptable thermoplastically workable polymers |
WO2012142634A1 (de) | 2011-04-18 | 2012-10-26 | Sunpor Kunststoff Gesellschaft M.B.H. | Flammgeschützte expandierbare polymerisate |
WO2012151596A2 (de) | 2011-04-18 | 2012-11-15 | Sunpor Kunststoff Gesellschaft M.B.H. | Expandierbare polymerisate aus celluloseacetatbutyrat und styrolpolymerisat |
EP2706086A1 (de) | 2012-09-05 | 2014-03-12 | Basf Se | Verfahren zur Herstellung von Schaumstoffplatten niedriger Dichte durch Extrusion von Styrolpolymeren unter Verwendung von Hydrofluorolefinen als Treibmittel |
Also Published As
Publication number | Publication date |
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BR112012005740A2 (pt) | 2019-09-24 |
PL2478044T3 (pl) | 2013-12-31 |
KR20120083406A (ko) | 2012-07-25 |
US20120178842A1 (en) | 2012-07-12 |
EP2478044A1 (de) | 2012-07-25 |
MX2012002896A (es) | 2012-04-02 |
CN102482445A (zh) | 2012-05-30 |
EP2478044B1 (de) | 2013-07-17 |
RU2012114679A (ru) | 2013-11-10 |
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