WO2006007995A2 - Procede pour produire du polystyrene expansible ignifuge - Google Patents

Procede pour produire du polystyrene expansible ignifuge Download PDF

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Publication number
WO2006007995A2
WO2006007995A2 PCT/EP2005/007398 EP2005007398W WO2006007995A2 WO 2006007995 A2 WO2006007995 A2 WO 2006007995A2 EP 2005007398 W EP2005007398 W EP 2005007398W WO 2006007995 A2 WO2006007995 A2 WO 2006007995A2
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WO
WIPO (PCT)
Prior art keywords
range
flame retardant
styrene
melt
polymer melt
Prior art date
Application number
PCT/EP2005/007398
Other languages
German (de)
English (en)
Other versions
WO2006007995A3 (fr
Inventor
Klaus Hahn
Gerd Ehrmann
Joachim Ruch
Markus Allmendinger
Bernhard Schmied
Jan Holoch
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to MX2007000052A priority Critical patent/MX2007000052A/es
Priority to EP05772383A priority patent/EP1771502A2/fr
Publication of WO2006007995A2 publication Critical patent/WO2006007995A2/fr
Publication of WO2006007995A3 publication Critical patent/WO2006007995A3/fr

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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
    • C08J9/0014—Use of organic additives
    • C08J9/0019—Use of organic additives halogenated
    • 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
    • B29C44/34—Auxiliary operations
    • B29C44/3461—Making or treating expandable particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/03—Extrusion of the foamable blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

Definitions

  • the invention relates to a process for the preparation of flame-retardant, expandable styrene polymers (EPS) by extrusion of a blowing agent and flame retardant-containing styrene polymer melt through a die plate with subsequent submerged water granulation.
  • EPS expandable styrene polymers
  • Processes for the preparation of flame-retardant, expandable styrenic polymers by extrusion of a blowing agent-containing styrenic polymer melt are e.g. from EP-A 0 981 574, WO 97/45477 or WO 03/46016.
  • the flameproofing agent is optionally melted together with other additives together with polystyrene and subsequently a blowing agent is added.
  • the polystyrene melt In order to homogeneously mix in the blowing agent and, if appropriate, further additives, the polystyrene melt generally has to be kept at temperatures well above the glass transition temperature of the polystyrene for a certain time. This can lead to the decomposition of a considerable proportion of the flame retardant added, which leads to discoloration and lesser effectiveness in the expandable polystyrene.
  • the object of the present invention was therefore to find an economical and gentle process for the preparation of flame-retardant, expandable styrene polymers.
  • EPS expandable styrene polymers
  • the melt temperature and residence time are selected according to the invention such that a homogeneous incorporation of the flame retardant is ensured and decomposition is minimized.
  • the melt temperature is preferably in the range from 140 to 220 ° C., preferably in the range from 160 to 210 ° C., particularly preferably in the range from 170 to 200 ° C.
  • the residence time of the flame retardant should be less than 30 minutes in the stated temperature ranges, preferably less than 15 minutes, particularly preferably less than 10 minutes.
  • the blowing agent is first mixed homogeneously into the styrene polymer melt, and then the flame retardant and, if appropriate, a flame-retardant synergist of the thickening-polymer-containing styrene polymer melt are metered in.
  • the flame retardant is preferably premixed in a side extruder with a proportion of polystyrene polymer melt and the styrene polymer melt is metered in the main stream.
  • the proportion of styrene polymer which is fed via the side extruder is less than 20% by weight.
  • the expandable styrene polymer preferably has a molecular weight in the range from 190,000 to 400,000 g / mol, more preferably in the range from 220,000 to 300,000 g / mol. Due to the reduction in molecular weight by shearing and / or temperature influence, the molecular weight of the expandable polystyrene is generally about 10,000 g / mol below the molecular weight of the polystyrene used.
  • the strand expansion after the nozzle exit should be as low as possible. It has been shown that the strand build-up can be influenced inter alia by the molecular weight distribution of the styrene polymer.
  • the expandable styrene polymer should therefore preferably have a molecular weight distribution with a polydispersity MJM n of at most 3.5, particularly preferably in the range from 1.5 to 3.0 and very particularly preferably in the range from 1.8 to 2.6.
  • styrene polymers preference is given 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 (SAN) Acrylonitrile-styrene-acrylic ester (ASA), methyl acrylate-butadiene-styrene (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) - polymers or mixtures thereof or with polyphenylene ether (PPE).
  • GPPS glassy polystyrene
  • HIPS toughened polystyrene
  • A-IPS anionically polymerized polystyrene or toughened polystyren
  • the styrene polymers mentioned can be used to improve the intrinsic mechanical properties or the thermal stability, 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), polyether sulfones (PES), polyether ketones or polyether sulfides (PES) or mixtures thereof, generally in proportions of not more than 30% by weight.
  • 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
  • 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 thermoplastic polymers mentioned, in particular styrene polymers and expandable styrene polymers (EPS) in amounts which do not significantly 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 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.
  • finely distributed internal water droplets can be introduced into the styrene polymer matrix. This can be done, for example, by the addition of water into 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.
  • 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 amount of blowing agent and water added is chosen so that the expandable styrene polymers (EPS) have an expansion capacity ⁇ , 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. When using fillers, depending on the type and amount of the filler, bulk densities in the range of 590 to 1200 g / l may occur.
  • the flame retardants used are organic bromine compounds having a bromine content of at least 70% by weight. Especially suitable are aliphatic, cycloaliphatic and aromatic bromine compounds, such as hexabromocyclododecane, penta bromomochlorocyclohexane, pentabromophenyl allyl ether.
  • the flame retardant is generally used in amounts of 0.2 to 5, preferably from 0.5 to 2.5 wt .-%, based on the styrene polymer.
  • the styrenic polymer melt dicumyl or dicumyl peroxide is preferably added as a flame-retardant synergist.
  • suitable flame retardant synergists are thermal free-radical formers having half-lives of 6 minutes at temperatures ranging from 110 to 300 0 C, preferably 140 to 23O 0 C, the fen liquid or in water, or Kohlenwasserstof ⁇ Weis oil are soluble.
  • Di-tert-butyl peroxide (Trigonox® B), tert-butyl hydroperoxide (Trigonox® A80), a solution of dicumyl peroxide in pentane or an aqueous solution of a peroxide or hydroperoxide are preferably used as the flame retardant synergist.
  • the flame retardant synergist is preferably pure or in the case of solids under normal conditions (1 bar, 23 0 C) is Scheme ⁇ nearly saturated solution, so it with classic pumping systems directly to a tempered and pressurized space can be dosed.
  • the flame-retardant synergist is used in amounts ranging from 0.05 to 1% by weight, preferably in the range from 0.1 to 0.5% by weight.
  • 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 or aluminum powder together or spatially separated, e.g. be added via mixer or side extruder.
  • 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 is mixed into the polymer melt.
  • the process comprises the stages a) melt production, b) mixing c) cooling d) conveying and e) granulation.
  • stages can be carried out by the apparatuses or apparatus combinations known in plastics processing.
  • static or dynamic mixers for example extruders, are suitable.
  • the polymer melt can be produced directly from be removed from a polymerization or directly produced in the mixing extruder or a separate Aufmmelzextruder by melting polymer granules.
  • the cooling of the melt can take place in the mixing units or in separate coolers.
  • For granulation for example, pressurized underwater granulation, granulation with rotating knives and cooling by spray-atomization of tempering liquids or sputtering granulation are considered.
  • Apparatus arrangements suitable for carrying out the method are, for example:
  • 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 supported at a temperature in the range of 140 to 300 0 C, preferably in the range of 160 to 240 0 C plate through the nozzle. 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 Polysty ⁇ rolschmelze.
  • the temperature of the nozzle plate is in the range of 20 to 100 0 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 of 0.2 to 1.5 mm, preferably in the range of 0.3 to 1.2 mm, particularly preferably in the range of 0.3 to 0.8 mm.
  • granule sizes of less than 2 mm, in particular in the range of 0.4 to 1.4 mm can be set in a targeted manner.
  • the strand expansion can be influenced, in addition to the molecular weight distribution, by the nozzle geometry.
  • the nozzle plate preferably has bores with a ratio L / D of at least 2, the length (L) designating the nozzle region whose diameter corresponds at most to the diameter (D) at the nozzle exit.
  • the ratio LJD is in the range of 3 - 20.
  • the diameter (E) of the holes at the nozzle inlet of the nozzle plate should be at least twice as large as the diameter (D) at the nozzle outlet.
  • An embodiment of the nozzle plate has bores with conical inlet and an inlet angle ⁇ less than 180 °, preferably in the range of 30 to 120 °.
  • the nozzle plate has bores with conical outlet and an outlet angle ß smaller than 90 °, preferably in the range of 15 to 45 °.
  • the nozzle plate can be equipped with bores of different outlet diameters (D). The various embodiments of the nozzle geometry can also be combined.
  • a particularly preferred process for the preparation of expandable Styrolpoly ⁇ mers comprises the steps
  • step g) the granulation can take place directly behind the nozzle plate under water at a pressure in the range of 1 to 25 bar, preferably 5 to 15 bar.
  • Shear rates are therefore particularly preferably below 50 / sec, preferably 5 to 30 / sec, and at temperatures below 260 0 C and short residence times in Be ⁇ range from 1 to 20, preferably 2 to 10 minutes, in stages) d to f) respected. It is especially preferred to use exclusively static mixers and static coolers throughout the process.
  • the polymer melt can be pumped and discharged by pressure pumps, eg gear pumps.
  • a further possibility for reducing the styrene monomer content and / or residual solvents, such as ethylbenzene, is to provide high degassing in step b) by means of entrainers, for example water, nitrogen or carbon dioxide, or to carry out the polymerization step a) anionically.
  • entrainers for example water, nitrogen or carbon dioxide
  • the anionic polymerization of styrene not only leads to styrene polymers with a low styrene monomer content, but at the same time to low styrene oligomer contents.
  • the residual styrene contents of the propellant-containing granules are surprisingly significantly reduced. Due to the peroxide addition, only a slight reduction in the average molecular weight is observed, but no substantial formation of oligomers or monomers is found. On the one hand, this makes it possible to use polystyrene melts having higher residual monomer contents, which in turn involves less expense in the degassing after the polystyrene reactor. On the other hand, starting from already largely degassed polystyrene, the residual monomer contents can be lowered even further. In this way, EPS granules can be achieved with residual monomer contents below 250 ppm.
  • the finished expandable styrene polymer granules can be coated by glycerol esters, antistatic agents or anticaking agents.
  • the EPS granules may be blended with 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 coating.
  • GMS typically 0.25%
  • 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 steam to foam particles having a density in the range of 8 to 100 g / l and welded in a second step in a closed mold to particle moldings. Examples:
  • Examples 2 and 4 used micronized HBCD with a mean particle size d (50) of 2 ⁇ m and micronized dicumyl with a mean particle size d (50) of 7 ⁇ m.
  • Example 1 was repeated except that HBCD and / or dicumyl as a flame retardant synergist were omitted.
  • HBCD was added to the polystyrene melt in the main stream at 22O 0 C prior to addition of the blowing agent.
  • the residence time of the HBCD at a temperature above 19O 0 C was 40 minutes.
  • the resulting EPS granules were colored very brown.
  • the expandable polystyrene granules obtained were prefoamed in flowing steam to form foam particles having a density of about 20 g / l and, after storage for 24 hours in gas-tight forms, welded to foam bodies by means of steam.
  • the fire behavior was determined.
  • the foam bodies were ignited in a horizontal fire test for 2 seconds with a Bunsen burner flame and then removed from the flame. Afterburning times of less than 6 seconds are suitable for passing the B2 test according to DIN 4102.
  • the amount of flame retardant (dosage and measured in the EPS particle foam) and the results of the fire protection test are summarized in Table 1.
  • Table 2 shows the foaming behavior of Examples 2 and 4 and Comparative Experiment V1.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Emergency Medicine (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

L'invention concerne un procédé pour produire des polymères de styrène expansible ignifugé (EPS) par extrusion d'une matière fondue, constituée d'un polymère de styrène, contenant un agent moussant et un agent ignifugeant, à travers une plaque porte-filière, puis par granulation sous l'eau, le temps de séjour de l'agent ignifugeant à une température de fusion située dans une plage allant de 140 à 220 °C étant inférieur à 30 minutes.
PCT/EP2005/007398 2004-07-15 2005-07-08 Procede pour produire du polystyrene expansible ignifuge WO2006007995A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
MX2007000052A MX2007000052A (es) 2004-07-15 2005-07-08 Metodo para la produccion de poliesterol expansible, a prueba de flama.
EP05772383A EP1771502A2 (fr) 2004-07-15 2005-07-08 Procede pour produire du polystyrene expansible ignifuge

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004034516.3 2004-07-15
DE102004034516A DE102004034516A1 (de) 2004-07-15 2004-07-15 Verfahren zur Herstellung von flammgeschütztem, expandierbarem Polystyrol

Publications (2)

Publication Number Publication Date
WO2006007995A2 true WO2006007995A2 (fr) 2006-01-26
WO2006007995A3 WO2006007995A3 (fr) 2006-04-06

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Application Number Title Priority Date Filing Date
PCT/EP2005/007398 WO2006007995A2 (fr) 2004-07-15 2005-07-08 Procede pour produire du polystyrene expansible ignifuge

Country Status (5)

Country Link
EP (1) EP1771502A2 (fr)
KR (1) KR20070042180A (fr)
DE (1) DE102004034516A1 (fr)
MX (1) MX2007000052A (fr)
WO (1) WO2006007995A2 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009033200A1 (fr) 2007-09-14 2009-03-19 Sunpor Kunststoff Ges.M.B.H. Procédé de production de polymérisats de styrène expansibles et leur utilisation
EP2062935A2 (fr) 2007-11-21 2009-05-27 Basf Se Procédé destiné à l'introduction de particules solides dans des masses fondues polymères
WO2009065880A2 (fr) * 2007-11-21 2009-05-28 Basf Se Polymères styréniques expansibles ignifugés et leur procédé de production
DE202010013851U1 (de) 2010-08-27 2010-12-16 Sunpor Kunststoff Gesellschaft M.B.H. Flammgeschützte, expandierbare Polymerisate
WO2013150456A1 (fr) 2012-04-06 2013-10-10 Versalis Spa Procédé pour l'insertion et le transport d'additifs labiles dans des flux de matériau fondu
EP2938661B1 (fr) 2012-12-28 2017-04-19 Total Research & Technology Feluy Polymères vinyliques aromatiques expansibles comprenant des plaquettes de coke aciculaire
EP2938662B1 (fr) 2012-12-28 2019-08-21 Total Research & Technology Feluy Polymères vinyliques aromatiques expansibles contenant des particules de graphite présentant une distribution polymodale de leur taille
US10639829B2 (en) 2015-01-14 2020-05-05 Synthos S.A. Process for the production of expandable vinyl aromatic polymer granulate having decreased thermal conductivity
US10808093B2 (en) 2015-01-14 2020-10-20 Synthos S.A. Combination of silica and graphite and its use for decreasing the thermal conductivity of vinyl aromatic polymer foam
US10961154B2 (en) 2015-01-14 2021-03-30 Synthos S.A. Geopolymer composite and expandable vinyl aromatic polymer granulate and expanded vinyl aromatic polymer foam comprising the same
US11440843B2 (en) 2016-07-20 2022-09-13 Synthos S.A. Modified geopolymer and modified geopolymer composite and process for the production thereof
US11859066B2 (en) 2015-01-14 2024-01-02 Synthos S.A. Use of a mineral having perovskite structure in vinyl aromatic polymer foam

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BRPI0709627A2 (pt) † 2006-03-22 2011-07-26 Basf Se processo e dispositivo para a granulaÇço de massas fundidas polimÉricas
EP2025700A1 (fr) * 2007-08-01 2009-02-18 Ineos Europe Limited procédé de fabrication de polystyrène expansible (eps) comprenant des retardateurs de flamme
PL2868686T3 (pl) * 2013-11-05 2019-06-28 Coperion Gmbh Sposób i urządzenie do wytwarzania stopionego polimeru zawierającego dodatki i środki porotwórcze
DK3475241T3 (da) 2016-07-20 2020-08-17 Synthos Dwory 7 Spolka Z Ograniczona Odpowiedzialnoscia Spolka Jawna Anvendelse af geopolymerisk tilsætningsstof i kombination med ikke-bromeret flammehæmmer i polymerskum
HUE056741T2 (hu) 2016-07-20 2022-03-28 Synthos Dwory 7 Spolka Z Ograniczona Odpowiedzialnoscia Spolka Jawna Eljárás geopolimer vagy geopolimer kompozit elõállítására

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EP0981574A1 (fr) 1997-05-14 2000-03-01 Basf Aktiengesellschaft Polymerisats de styrene expansibles contenant des particules de graphite
DE19819058A1 (de) 1998-04-29 1999-11-04 Basf Ag Teilchenförmige expandierbare Styrolpolymerisate
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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009033200A1 (fr) 2007-09-14 2009-03-19 Sunpor Kunststoff Ges.M.B.H. Procédé de production de polymérisats de styrène expansibles et leur utilisation
EP2062935A2 (fr) 2007-11-21 2009-05-27 Basf Se Procédé destiné à l'introduction de particules solides dans des masses fondues polymères
WO2009065880A2 (fr) * 2007-11-21 2009-05-28 Basf Se Polymères styréniques expansibles ignifugés et leur procédé de production
WO2009065880A3 (fr) * 2007-11-21 2009-09-24 Basf Se Polymères styréniques expansibles ignifugés et leur procédé de production
US8222307B2 (en) 2007-11-21 2012-07-17 Basf Se Flameproof expandable styrene polymers, and method for the production thereof
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WO2012024709A1 (fr) 2010-08-27 2012-03-01 Sunpor Kunststoff Ges.M.B.H. Polymères thermo-isolants ignifugés et leur procédé de production
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WO2013150456A1 (fr) 2012-04-06 2013-10-10 Versalis Spa Procédé pour l'insertion et le transport d'additifs labiles dans des flux de matériau fondu
EP2938661B1 (fr) 2012-12-28 2017-04-19 Total Research & Technology Feluy Polymères vinyliques aromatiques expansibles comprenant des plaquettes de coke aciculaire
EP2938662B1 (fr) 2012-12-28 2019-08-21 Total Research & Technology Feluy Polymères vinyliques aromatiques expansibles contenant des particules de graphite présentant une distribution polymodale de leur taille
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US11708306B2 (en) 2015-01-14 2023-07-25 Synthos S.A. Geopolymer composite and expandable vinyl aromatic polymer granulate and expanded vinyl aromatic polymer foam comprising the same
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EP1771502A2 (fr) 2007-04-11
DE102004034516A1 (de) 2006-02-16
KR20070042180A (ko) 2007-04-20
MX2007000052A (es) 2007-03-28
WO2006007995A3 (fr) 2006-04-06

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