EP2513209A1 - Flammgeschützte polymerschaumstoffe - Google Patents
Flammgeschützte polymerschaumstoffeInfo
- Publication number
- EP2513209A1 EP2513209A1 EP10787495A EP10787495A EP2513209A1 EP 2513209 A1 EP2513209 A1 EP 2513209A1 EP 10787495 A EP10787495 A EP 10787495A EP 10787495 A EP10787495 A EP 10787495A EP 2513209 A1 EP2513209 A1 EP 2513209A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- flame
- polymer
- retardant
- styrene
- range
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0019—Use of organic additives halogenated
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- 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
- C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
-
- 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
- C08J9/20—Making expandable particles by suspension polymerisation in the presence of the blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions 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; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
-
- 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
- C09K21/14—Macromolecular materials
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
-
- 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
- C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
-
- 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
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/136—Phenols containing halogens
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Definitions
- the invention relates to flame-retardant polymer foams which contain at least one halogenated polymer as flame retardants, to processes for their preparation and to flame-retardant expandable styrene polymers.
- 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
- halogenated, in particular brominated, organic compounds have been used for polystyrene homopolymers and copolymers.
- HBCD hexabromocyclododecane
- Halogen-free flame retardants must be used to achieve the same flame retardancy of halogen-containing flame retardants usually in significantly higher amounts. Therefore, halogen-containing flame retardants which 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. Moreover, in the production of expandable polystyrene by suspension polymerization, the high levels of flame retardant can reduce the stability of the suspension.
- WO 2007/058736 describes thermally stable, brominated butadiene-styrene copolymers as alternative flame retardants to hexabromocyclodocecane (HBCD) in styrene polymers and extruded polystyrene foam boards (XPS).
- HBCD hexabromocyclodocecane
- JP-A 2007-238926 describes thermoplastic foams with high heat resistance, which are equipped for flame retardancy with brominated flame retardants, which have a weight loss of 5% at temperatures above 270 ° C in the thermogravimetic analysis.
- the object of the invention was therefore to find a flame retardant for polymer foams, in particular for expandable polystyrene (EPS) or polystyrene extrusion foam boards (XPS), which the foaming process and the me- chan properties is not materially affected, in terms of environmental and health hazards harmless and especially in small quantities sufficient flame retardancy in polymer foams allows.
- the flame retardant should have a high thermal resistance or show little influence on regulators and initiators in the suspension polymerization.
- the halogenated polymer used as flame retardant preferably has an average molecular weight in the range from 5,000 to 300,000, in particular 30,000 to 150,000, determined by gel permeation chromatography (GPC).
- the halogenated polymer has a weight loss of 5 wt .-% at a temperature of 250 ° C or higher, preferably in the range of 270 to 370 ° C in the thermogravimetric analysis (TGA).
- TGA thermogravimetric analysis
- Preferred halogenated polymers have a bromine content in the range of 0 to 80 weight percent, preferably 10 to 75 weight percent, and a chlorine content in the range of 0 to 50 weight percent, preferably 1 to 25 weight percent, based on the halogenated polymer.
- Preferred halogenated polymers as flame retardants are brominated polystyrene or styrene-butadiene block copolymer having a bromine content in the range from 40 to 80% by weight.
- Further preferred halogenated polymers as flame retardants are polymers which contain tetrabromobisphenol A units (TBBPA), for example tetrabromophenyl. bisphenol A diglycidyl ether compounds (CAS number 68928-70-1 or 135229-48-0).
- TBPA tetrabromobisphenol A units
- bisphenol A diglycidyl ether compounds CAS number 68928-70-1 or 135229-48-0.
- the flame-retardant polymer foams according to the invention generally contain the halogenated polymers in an amount in the range from 0.2 to 25% by weight, preferably in the range from 1 to 15% by weight, based on the polymer foam.
- the effectiveness of the halogenated polymers 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.
- suitable flame retardant synergists are zinc compounds or antimony trioxide. In this case, 0.05 to 5 parts by weight of the flame retardant synergists are usually used in addition to the halogenated polymer.
- flame retardants such as melamine, melamine cyanurates, metal oxides, metal hydroxides, phosphates, phosphinates or expandable graphite can also 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 ,
- the flame-retardant polymer foams preferably have a density in the range from 5 to 200 kg / m 3 , more 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 polymer matrix of the flameproofed polymer foams preferably consists of thermoplastic polymers or polymer mixtures, in particular styrene polymers.
- the flame retardant, expandable styrenic polymers (EPS) and styrenic polymer extrusion foams (XPS) of the present invention may be admixed by blending a propellant and the halogenated polymer into the polymer melt and then extruding and granulating under pressure to expandable granules (EPS) or by extrusion and relaxation using appropriately shaped nozzles Foam boards (XPS) or foam strands are processed.
- Expandable styrene polymers (EPS) are understood to mean propellant-containing styrene polymers.
- the EPS particle size is preferably in the range of 0.2 to 2 mm.
- Styrenic polymer particulate foams are obtainable by prefoaming and sintering the corresponding expandable styrene polymers (EPS).
- EPS expandable styrene polymers
- the styrene polymer particle foams preferably have 2 to 15 cells / mm.
- the expandable styrene polymer preferably has an average 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 refractometry detection (RI) over polystyrene standards. Due to the reduction in molecular weight by shear and / or the effect of temperature, the molecular weight of the expandable polystyrene in the extrusion processes is generally about 10,000 g / mol below the molecular weight of the polystyrene used.
- styrene polymers to glassy polystyrene (GPPS), toughened polystyrene (HIPS), anionically polymerized polystyrene or toughened polystyrene (A-IPS), styrene-a-methstyrene copolymers, acrylonitrile-butadiene-styrene polymers (ABS), styrene-acrylonitrile polymer (SAN) acrylonitrile-styrene-acrylic esters (ASA), styrene acrylates such as styrene-methyl acrylate (SMA) and styrene-methyl methacrylate (SMMA), methyl acrylate-butadiene-styrene (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) -polymerizates, styrene rol-N-phenylmaleimi
- the styrene polymers mentioned can be used to improve the mechanical properties or the temperature resistance, if appropriate by 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% by weight in total , preferably in the range of 1 to 10 wt .-%, based on the polymer melt, mixed.
- thermoplastic polymers such as polyamides (PA), polyolefins, such as polypropylene (PP) or polyethylene (PE), polyacrylates, such as polymethyl methacrylate (PMMA), Polycarbonate (PC), polyesters,
- mixtures in the above amounts ranges with z.
- rubbers such as polyacrylates or polydienes, z.
- Suitable compatibilizers are e.g. Maleic anhydride-modified styrene copolymers, polymers or organosilanes containing epoxide groups.
- the styrene polymers may also be blended in the production process with polymer recyclates of the aforementioned 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 from 1 to 20% by weight.
- EPS expandable styrene polymers
- the acrylonitrile content in SAN is preferably 25 to 33 wt .-%.
- the methacrylate content in SMA is preferably 25 to 30 wt .-%.
- Particularly preferred flame-retardant polymer foams contain mixtures of SAN and SMA as polymer matrix, TBBPA compounds as flame retardant and antimony trioxide as flame retardant synergist.
- 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 CO2 or mixtures with alcohols or ketones.
- finely distributed 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 mixers. 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 ⁇ form during foaming foams with sufficient cell count and homogeneous foam structure.
- the amount of blowing agent and water added is chosen such that the expandable styrene polymers (EPS) have an expansion capacity, defined as bulk density before foaming / bulk density after foaming, of 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.
- bulk densities in the range of 590 to 1200 g / l may occur.
- the styrene polymers may contain the customary and known auxiliaries and additives, for example flame retardants, fillers, nucleating agents, UV stabilizers, chain transfer agents, blowing agents, plasticizers, antioxidants, soluble and insoluble inorganic and / or organic dyes and pigments, for example infrared (IR) - Absorber, such as carbon black, graphite or aluminum powder.
- auxiliaries and additives for example flame retardants, fillers, nucleating agents, UV stabilizers, chain transfer agents, blowing agents, plasticizers, antioxidants, soluble and insoluble inorganic and / or organic dyes and pigments, for example infrared (IR) - Absorber, such as carbon black, graphite or aluminum powder.
- IR infrared
- 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 styrenic 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 amount of IR absorber used depends on their nature and effect.
- the styrene polymer particle foam preferably contain 0.5 to 5 wt .-%, particularly preferably 1 to 4 wt .-% IR absorber.
- the IR absorber are graphite, carbon black or aluminum having an average particle size in the range from 1 to 50 ⁇ m.
- the preferably used graphite preferably has an average particle size of 1 to 50 ⁇ m, in particular of 2.5 to 12 ⁇ m, a bulk density of 100 to 500 g / l and a specific surface area of 5 to 20 m 2 / g. It can be used natural graphite or ground synthetic graphite.
- the graphite particles are contained in the styrene polymer preferably in amounts of 0.05 to 8 wt .-%, in particular from 0.1 to 5 wt .-%.
- a problem with the use of graphite particles is the easy flammability of the graphite particles containing polystyrene particulate foams.
- the above-mentioned flame retardants are added to the expandable styrene polymers according to the invention. Surprisingly, these flame retardants do not lead to any impairment of the mechanical characteristics of the polystyrene particle foams containing carbon black or graphite.
- the IR absorber-containing styrene polymer particle foams even at densities in the range of 7 to 20 g / l, preferably in the range of 10 to 16 g / l, a thermal conductivity ⁇ , determined at 10 ° C according to DIN 52612, below 32 mW / m * K, preferably in the range from 27 to 31, particularly preferably in the range from 28 to 30 mW / m * K.
- the low thermal conductivities are achieved even when the blowing agent has substantially diffused out of the cells, i. H. the cells are filled with a gas which consists of at least 90% by volume, preferably 95 to 99% by volume, of an inorganic gas, in particular of air.
- EPS expandable styrene polymers
- the athermanous particles and a nonionic surfactant are mixed with a melt of the styrene polymer, preferably in an extruder.
- the blowing agent is added to the melt.
- the athermanous particles can also be introduced into a melt of propellant-containing styrene polymers. incorporating sat, expediently segregated edge fractions of a bead spectrum of resulting in a suspension polymerization propellant-containing polystyrene beads are used.
- the polystyrene melt containing the blowing agents and athermanous particles are pressed out and reduced to granules containing blowing agent.
- the athermanous particles can have a strong nucleating effect, after pressing under pressure, they should be cooled rapidly in order to avoid foaming. It is therefore advisable to carry out underwater granulation under pressure in a closed system. It is also possible, the athermane particle-containing styrene polymers
- the granules are then preferably impregnated in aqueous suspension with the blowing agent.
- the athermanous particles can also be added to the melt in the form of a concentrate in polystyrene.
- polystyrene granules and athermanous particles are preferably introduced together into an extruder, the polystyrene melted and mixed with the athermanous particles.
- the athermanous particles and a nonionic surfactant in the suspension polymerization, provided they are sufficiently inert to the water used as a suspension medium in the rule. They may in this case be added to the monomeric styrene before suspension or may be added to the reaction batch in the course of the course of the first half of the polymerization cycle.
- the blowing agent is preferably added in the course of the polymerization, but it may also be incorporated afterwards the styrene polymer.
- non-recyclable edge fractions have diameters larger than 2.0 mm and smaller than 0.2 mm, respectively.
- Polystyrene recyclate and foam polystyrene recyclate can also be used.
- prepolymer is prepolymerized in substance to a conversion of 0.5 to 70% and the prepolymer is supendiert and polymerized together with the athermanen particles in the aqueous phase.
- the expandable styrene polymers are particularly preferably prepared by polymerization of styrene and optionally copolymerizable monomers in aqueous suspension and impregnation with a blowing agent, wherein the polymerization in the presence of 0.1 to 5 wt .-% graphite particles, based on the styrene polymer, and a nonionic surfactant is performed.
- Suitable nonionic surfactants include, for example, maleic anhydride copolymers (MSA), e.g. from maleic anhydride and C2o-24-1-olefin, polyisobutylene succinic anhydrides (PIBSA) or their reaction products with hydroxy-polyethylene glycol esters, diethylaminoethanol or amines, such as tridecylamine, octylamine or polyetheramine, tetraethylenepentaamine or mixtures thereof.
- the molecular weights of the nonionic surfactant are preferably in the range of 500 to 3000 g / mol. They are usually used in amounts ranging from 0.01 to 2 wt .-%, based on styrene polymer.
- the expandable, athermanous particle-containing styrene polymers can be processed into polystyrene foams having densities of 5 to 35 g / l, preferably from 8 to 25 g / l and especially from 10 to 15 g / l.
- 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 forms that do not close in a gas-tight manner and subjected to steam. After cooling, the moldings can be removed.
- the foams produced from the expandable styrene polymers according to the invention are distinguished by outstanding thermal insulation. This effect is particularly evident at low densities.
- the foams can be used for thermal insulation of buildings and parts of buildings, for thermal insulation of machinery and household appliances as well as packaging materials.
- 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 take place 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 to at least 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 flame-retardant, expandable styrene polymers
- EPS 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 usual adjuvants e.g. Peroxide initiators, suspension stabilizers, blowing agents, chain transfer agents, expanding aids, nucleating agents and plasticizers.
- the cyclic or acyclic halogenated polymer according to the 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. It is advantageous to use as suspension stabilizers inorganic Pickering dispersants, e.g. Magnesium pyrophosphate or calcium phosphate use.
- the finished expandable styrene polymer granules can be coated with the customary and known coating agents, for example metal stearates, glycerol esters and finely divided silicates, antistatic agents or anticaking agents.
- the customary and known coating agents for example metal stearates, glycerol esters and finely divided silicates, antistatic agents or anticaking agents.
- the EPS granules may contain glycerol monostearate GMS (typically 0.25%), glycerol tristearate (typically 0.25%) finely divided silica Aerosil R972 (typically 0.12%) and Zn stearate (typically 0.15%), and antistatic be coated.
- the expandable styrene polymer granules according to the invention can be prefoamed in a first step by means of hot air or steam into 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 forms that do not close in a gas-tight manner and subjected to steam. After cooling, the moldings can be removed.
- FRT 1 brominated polystyrene having a bromine content of about 66 wt .-% and a
- the fire behavior of the foam boards was determined at a foam density of 15 kg / m 3 according to DIN 4102
- Examples 1 to 4 and Comparative Experiments V1 to V4 In a pressure-resistant stirred tank, a mixture of 150 parts of deionized water, 0.1 parts of sodium pyrophosphate, 100 parts of styrene, 0.45 parts of tert. Butyl peroxy-2-ethylhexanoate, 0.2 part ter-butyl perbenzoate, 5 parts goiter mill The powdered graphite UFT 99.5 and 3 parts of the flame retardants indicated in the table are heated to 90 ° C. with stirring. In some examples, in addition to the flame retardants, 0.2 part by weight of dicumyl or dicumyl peroxide was additionally added as a flame retardant synergist.
- the obtained expandable polystyrene beads were washed with demineralized water, sieved between 0.7-1.0 mm and then dried with hot air (30 ° C).
- the beads were prefoamed by the action of flowing steam and, after 12 hours' storage, were further sealed by a further treatment with steam in a closed mold to form foam blocks with a density of 15 kg / m3!
- the determination of the viscosity numbers VZ (0.5% in toluene at 25 ° C) was carried out according to DIN 53 726
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102009059781A DE102009059781A1 (de) | 2009-12-18 | 2009-12-18 | Flammgeschützte Polymerschaumstoffe |
PCT/EP2010/069528 WO2011073141A1 (de) | 2009-12-18 | 2010-12-13 | Flammgeschützte polymerschaumstoffe |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2513209A1 true EP2513209A1 (de) | 2012-10-24 |
Family
ID=43629483
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP10787495A Withdrawn EP2513209A1 (de) | 2009-12-18 | 2010-12-13 | Flammgeschützte polymerschaumstoffe |
Country Status (10)
Country | Link |
---|---|
US (1) | US20120252914A1 (zh) |
EP (1) | EP2513209A1 (zh) |
JP (1) | JP2013514397A (zh) |
KR (1) | KR20120107114A (zh) |
CN (1) | CN102656220A (zh) |
BR (1) | BR112012014976A2 (zh) |
DE (1) | DE102009059781A1 (zh) |
MX (1) | MX2012006808A (zh) |
RU (1) | RU2012130168A (zh) |
WO (1) | WO2011073141A1 (zh) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018069186A1 (en) | 2016-10-10 | 2018-04-19 | Total Research & Technology Feluy | Improved expandable vinyl aromatic polymers |
WO2018069178A1 (en) | 2016-10-10 | 2018-04-19 | Total Research & Technology Feluy | Improved expandable vinyl aromatic polymers |
WO2018069185A1 (en) | 2016-10-10 | 2018-04-19 | Total Research & Technology Feluy | Improved expandable vinyl aromatic polymers |
WO2021043552A1 (en) | 2019-09-04 | 2021-03-11 | Total Research & Technology Feluy | Expandable vinyl aromatic polymers with improved flame retardancy |
RU2802716C1 (ru) * | 2022-10-14 | 2023-08-31 | Публичное акционерное общество "СИБУР Холдинг" | Модифицированный диенсодержащий (cо)полимер и применение его в качестве антипирена в полимерных и битумных композициях |
Families Citing this family (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10183426B2 (en) | 2009-05-26 | 2019-01-22 | Basf Se | Water as a propellant for thermoplastics |
JP2014520929A (ja) * | 2011-07-14 | 2014-08-25 | ダウ グローバル テクノロジーズ エルエルシー | 臭素化ビニル芳香族−ブタジエンコポリマーを含有する耐衝撃性改良スチレン系ポリマー |
JP2013116958A (ja) | 2011-12-02 | 2013-06-13 | Dow Global Technologies Llc | 発泡性スチレン系樹脂組成物及びスチレン系樹脂発泡体の製造方法 |
EP2794740A2 (de) * | 2011-12-21 | 2014-10-29 | Basf Se | Verfahren zur herstellung von expandierbaren, graphit- und flammschutzmittelhaltigen styrolpolymerisaten |
NL2009320C2 (nl) * | 2012-08-14 | 2014-02-18 | Synbra Tech Bv | Deeltjesvormig, expandeerbaar polymeer, werkwijze ter vervaardiging hiervan, alsmede de toepassing. |
WO2014066089A1 (en) * | 2012-10-24 | 2014-05-01 | Dow Global Technologies Llc | Glycerol ester and brominated polymer in styrenic polymer |
EP2938662B1 (en) | 2012-12-28 | 2019-08-21 | Total Research & Technology Feluy | Expandable vinyl aromatic polymers containing graphite particles having a polymodal particle size distribution |
EP2945981B1 (en) | 2013-01-18 | 2020-05-06 | BEWiSynbra RAW Oy | Method of producing polystyrene beads containing athermanous particles |
WO2014125933A1 (ja) * | 2013-02-14 | 2014-08-21 | 株式会社カネカ | スチレン系樹脂押出発泡体及びそのリサイクル方法 |
EP2789651A1 (de) | 2013-04-11 | 2014-10-15 | Basf Se | Flammschutzmittelzusammensetzung zur Verwendung in Styrolpolymerschaumstoffen |
JP6156060B2 (ja) * | 2013-10-29 | 2017-07-05 | 株式会社ジェイエスピー | 発泡性複合樹脂粒子の製造方法 |
JP6273001B2 (ja) * | 2013-10-30 | 2018-01-31 | ダウ グローバル テクノロジーズ エルエルシー | 臭素化スチレン−ブタジエンコポリマーを含有し、かつ向上したセルサイズ均一性を有する発泡スチレンポリマー |
EP3070118B1 (en) | 2013-11-14 | 2020-02-26 | Kaneka Corporation | Extruded styrenic resin foam and method for manufacturing same |
JP6349697B2 (ja) * | 2013-11-27 | 2018-07-04 | 株式会社ジェイエスピー | 発泡性ポリスチレン系樹脂粒子の製造方法 |
JP6263987B2 (ja) * | 2013-11-27 | 2018-01-24 | 株式会社ジェイエスピー | 発泡性ポリスチレン系樹脂粒子の製造方法 |
JP6220663B2 (ja) * | 2013-12-17 | 2017-10-25 | 株式会社カネカ | 難燃性を付与した発泡性スチレン系樹脂粒子とその製造方法 |
CA2938673A1 (en) * | 2014-02-03 | 2015-08-06 | Dow Global Technologies Llc | Stable styrenic foam with brominated styrene/butadiene copolymer and metal oxide infrared attenuator |
JP6555251B2 (ja) * | 2014-03-10 | 2019-08-07 | 株式会社カネカ | スチレン系樹脂発泡成形体及びその製造方法 |
EP2957413A1 (de) | 2014-06-18 | 2015-12-23 | Basf Se | Verfahren zur entgasung von flammgeschützten, treibmittelhaltigen polymergranulaten oder flammgeschützten schaumstoffrecyclaten |
EP2957595A1 (de) | 2014-06-18 | 2015-12-23 | Basf Se | Flammschutzmittelzusammensetzung zur Verwendung in Styrolpolymerschaumstoffen |
JP6405781B2 (ja) * | 2014-08-08 | 2018-10-17 | 株式会社ジェイエスピー | 発泡性スチレン系樹脂粒子及びその製造方法 |
CN104194031B (zh) * | 2014-08-26 | 2016-12-07 | 北京工商大学 | 一种含阻燃剂的可发聚苯乙烯颗粒的制备方法 |
JP6409642B2 (ja) * | 2015-03-24 | 2018-10-24 | 株式会社ジェイエスピー | 発泡性複合樹脂粒子 |
KR102567360B1 (ko) * | 2015-09-09 | 2023-08-17 | 가부시키가이샤 가네카 | 발포성 스티렌계 수지 입자, 스티렌계 수지의 예비 발포 입자, 스티렌계 수지 발포 성형체 및 발포성 수지 입자의 제조 방법 |
CN109312108A (zh) | 2016-05-11 | 2019-02-05 | 欧文斯科宁知识产权资产有限公司 | 包含低水平溴化阻燃剂的聚合物泡沫及其制备方法 |
JP6306643B2 (ja) * | 2016-06-08 | 2018-04-04 | 株式会社カネカ | 発泡性スチレン系樹脂粒子とその製造方法、スチレン系樹脂発泡成形体 |
IT201600071347A1 (it) | 2016-07-08 | 2018-01-08 | Versalis Spa | Composizioni espandibili contenenti polimeri vinil aromatici aventi proprietà autoestinguenti e migliorata processabilità |
WO2018105394A1 (ja) * | 2016-12-07 | 2018-06-14 | 三菱電機株式会社 | 発泡断熱材の製造方法および発泡断熱材 |
EP3778741A4 (en) * | 2018-04-11 | 2021-05-19 | Kaneka Corporation | EXPANDABLE PARTICLES OF THERMOPLASTIC RESIN |
KR102621597B1 (ko) * | 2018-09-10 | 2024-01-08 | 에스케이이노베이션 주식회사 | 난연제 및 이를 포함하는 난연성 수지 조성물 |
KR102319646B1 (ko) * | 2019-06-27 | 2021-11-05 | (주)동인산업 | 건축용 발포 단열재 |
CN115485325A (zh) * | 2020-04-21 | 2022-12-16 | 巴斯夫欧洲公司 | 包含聚合的溴化阻燃剂的可膨胀苯乙烯聚合物 |
CN114133675B (zh) * | 2021-12-13 | 2024-02-06 | 无锡格利斯环保科技有限公司 | 一种阻燃性好的聚苯乙烯泡沫材料及其制备工艺 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1218149C2 (de) * | 1959-08-22 | 1974-12-19 | Basf Ag | Flammschutzmittel fuer kunststoffe |
US3316188A (en) * | 1959-11-16 | 1967-04-25 | Bell & Richardson Inc De | Dielectric lens material comprising a halogenated epoxy resin composition and a polymerized vegetable oil derived polyamide resin |
US3063954A (en) * | 1960-10-25 | 1962-11-13 | Koppers Co Inc | Process for producing flame-retardant expandable polystyrene particles |
US4542164A (en) * | 1982-10-04 | 1985-09-17 | Toray Industries, Incorporated | Flame-retardant polyolefin foam |
CA2136879A1 (en) * | 1993-12-16 | 1995-06-17 | John E. Hayes | Halogenated polyaromatic resins as flame retardant additives for polyurethane compositions |
DE19742910A1 (de) * | 1997-09-29 | 1999-04-01 | Basf Ag | Verfahren zur Herstellung von expandierbaren Styrolpolymerisaten |
DE102004034514A1 (de) * | 2004-07-15 | 2006-02-16 | Basf Ag | Synergistische Flammschutzmischungen für Polystyrolschaumstoffe |
EP1924641A1 (en) * | 2005-08-08 | 2008-05-28 | Albermarle Corporation | Flame retarded styrenic polymer foams and foam precursors |
WO2007058736A1 (en) * | 2005-11-12 | 2007-05-24 | Dow Global Technologies Inc. | Brominated butadiene/vinyl aromatic copolymers, blends of such copolymers with a vinyl aromatic polymer, and polymeric foams formed from such blends |
JP5042653B2 (ja) | 2006-02-07 | 2012-10-03 | 株式会社カネカ | 熱可塑性樹脂発泡体 |
NL1037008C2 (nl) * | 2009-06-02 | 2010-12-07 | Synbra Tech Bv | Deeltjesvormig, expandeerbaar polystyreen alsmede een werkwijze ter bereiding daarvan. |
-
2009
- 2009-12-18 DE DE102009059781A patent/DE102009059781A1/de not_active Withdrawn
-
2010
- 2010-12-13 WO PCT/EP2010/069528 patent/WO2011073141A1/de active Application Filing
- 2010-12-13 US US13/515,962 patent/US20120252914A1/en not_active Abandoned
- 2010-12-13 RU RU2012130168/05A patent/RU2012130168A/ru unknown
- 2010-12-13 BR BR112012014976A patent/BR112012014976A2/pt not_active Application Discontinuation
- 2010-12-13 EP EP10787495A patent/EP2513209A1/de not_active Withdrawn
- 2010-12-13 MX MX2012006808A patent/MX2012006808A/es unknown
- 2010-12-13 CN CN2010800574449A patent/CN102656220A/zh active Pending
- 2010-12-13 KR KR1020127018693A patent/KR20120107114A/ko not_active Application Discontinuation
- 2010-12-13 JP JP2012543659A patent/JP2013514397A/ja not_active Withdrawn
Non-Patent Citations (1)
Title |
---|
See references of WO2011073141A1 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018069186A1 (en) | 2016-10-10 | 2018-04-19 | Total Research & Technology Feluy | Improved expandable vinyl aromatic polymers |
WO2018069178A1 (en) | 2016-10-10 | 2018-04-19 | Total Research & Technology Feluy | Improved expandable vinyl aromatic polymers |
WO2018069185A1 (en) | 2016-10-10 | 2018-04-19 | Total Research & Technology Feluy | Improved expandable vinyl aromatic polymers |
US11834563B2 (en) | 2016-10-10 | 2023-12-05 | Totalenergies Onetech Belgium | Expandable vinyl aromatic polymers |
WO2021043552A1 (en) | 2019-09-04 | 2021-03-11 | Total Research & Technology Feluy | Expandable vinyl aromatic polymers with improved flame retardancy |
RU2802716C1 (ru) * | 2022-10-14 | 2023-08-31 | Публичное акционерное общество "СИБУР Холдинг" | Модифицированный диенсодержащий (cо)полимер и применение его в качестве антипирена в полимерных и битумных композициях |
Also Published As
Publication number | Publication date |
---|---|
US20120252914A1 (en) | 2012-10-04 |
JP2013514397A (ja) | 2013-04-25 |
KR20120107114A (ko) | 2012-09-28 |
DE102009059781A1 (de) | 2011-06-22 |
BR112012014976A2 (pt) | 2016-04-05 |
RU2012130168A (ru) | 2014-01-27 |
WO2011073141A1 (de) | 2011-06-23 |
MX2012006808A (es) | 2012-08-03 |
CN102656220A (zh) | 2012-09-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2011073141A1 (de) | Flammgeschützte polymerschaumstoffe | |
EP1791896B8 (de) | Halogenfreie, flammgeschützte polymerschaumstoffe | |
EP1758951B1 (de) | Styrolpolymer-partikelschaumstoffe mit verringerter wärmeleitfähigkeit | |
EP2212377B1 (de) | Flammgeschützte expandierbare styrolpolymere und verfahren zu ihrer herstellung | |
EP1694753A1 (de) | Partikelschaumformteile aus expandierbaren styrolpolymeren und mischungen mit thermoplastischen polymeren | |
EP1694754A1 (de) | Partikelschaumstoffformteile aus expandierbaren, füllstoff enthaltenden polymergranulaten | |
WO2006058733A1 (de) | Expandierbare styrolpolymergranulate und partikelschaumstoffe mit verringerter wärmeleitfähigkeit | |
EP1771502A2 (de) | Verfahren zur herstellung von flammgesch]tztem, expandierbarem polystyrol | |
EP2274369B1 (de) | Ps-schaumstoffe mit geringem metallgehalt | |
WO2006007996A1 (de) | Synergistische flammschutzmischungen für polystyrolschaumstoffe | |
EP2531552A2 (de) | Halogenfreie, phosphorhaltige flammgeschützte polymerschaumstoffe | |
EP1616902B1 (de) | Selbstverlöschender Styrolpolymer-Partikelschaumstoff | |
EP1694755A1 (de) | Expandierbare styrolpolymergranulate mit bi- oder multimodaler molekulargewichtsverteilung | |
DE102004034527A1 (de) | Verfahren zur Herstellung von expandierbaren Styrolpolymeren mit verbesserter Expandierbarkeit | |
DE10358798A1 (de) | Expandierbare Styrolpolymergranulate | |
EP1846486A1 (de) | Flammgeschützte, expandierbare styrolpolymer (eps)-granulate mit flammschutzsynergist in der beschichtung | |
DE10358805A1 (de) | Partikelschaumformteile aus expandierbaren, schlagzähmodifizierten, thermoplastischen Polymergranulaten | |
WO2005056654A1 (de) | Expandierbare styrolpolymergranulate |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20120718 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
DAX | Request for extension of the european patent (deleted) | ||
17Q | First examination report despatched |
Effective date: 20130709 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20131120 |