EP2307497A1 - Expandierbares thermoplastisches polymerblend - Google Patents

Expandierbares thermoplastisches polymerblend

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Publication number
EP2307497A1
EP2307497A1 EP09781151A EP09781151A EP2307497A1 EP 2307497 A1 EP2307497 A1 EP 2307497A1 EP 09781151 A EP09781151 A EP 09781151A EP 09781151 A EP09781151 A EP 09781151A EP 2307497 A1 EP2307497 A1 EP 2307497A1
Authority
EP
European Patent Office
Prior art keywords
block
polymer
polymer blend
blend according
weight
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Withdrawn
Application number
EP09781151A
Other languages
German (de)
English (en)
French (fr)
Inventor
Carsten Schips
Klaus Hahn
Konrad Knoll
Holger Ruckdaeschel
Jens Assmann
Helmut Winterling
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BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP09781151A priority Critical patent/EP2307497A1/de
Publication of EP2307497A1 publication Critical patent/EP2307497A1/de
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/12Powdering or granulating
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00Compositions 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
    • C08L25/02Homopolymers or copolymers of hydrocarbons
    • C08L25/04Homopolymers or copolymers of styrene
    • C08L25/06Polystyrene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00Characterised 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
    • C08J2325/02Homopolymers or copolymers of hydrocarbons
    • C08J2325/04Homopolymers or copolymers of styrene
    • C08J2325/06Polystyrene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2453/00Characterised 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12Polyphenylene oxides

Definitions

  • the invention relates to an expandable thermoplastic polymer blend, to granules obtainable from the polymer blend, to a process for the preparation of the polymer blend and to foams.
  • expanded and expandable styrene polymers can be prepared by means of extrusion processes.
  • the propellant is e.g. is mixed into the polymer melt via an extruder, conveyed through a die plate and granulated to particle strands or strands (US-A-3,817,669, GB-A-1, 062,307, EP-B 0 126 459, US-A-5,000,891).
  • EP-A 668 139 describes a process for the production of expandable polystyrene granules (EPS) wherein the propellant-containing melt is produced by means of static mixing elements in a dispersing, holding and cooling step and then granulated. Due to the cooling of the melt to a few degrees above the solidification temperature, the removal of high amounts of heat is necessary.
  • EPS expandable polystyrene granules
  • EPS expandable styrene polymers
  • Expandable, rubber-modified styrene polymers for elastic polystyrene foams are described, for example, in WO 94/25516, EP-A 682 077, DE-A 197 10 442 and EP-A 0 872 513.
  • WO 2005/06652 are particle foam moldings having a density of 10 to 100 g / l, by welding prefoamed foam particles of expandable thermoplastic polymer granules containing 5 to 100 wt .-% of a styrene copolymer A), 0 to 95 parts by weight.
  • styrene B % Polystyrene B) and 0 to 95% by weight of a thermoplastic polymer C) other than A) and B), and processes for producing the expandable thermoplastic polymer granules.
  • styrene copolymer A for example, styrene-acrylonitrile copolymers (SAN) are described.
  • the invention is an expandable thermoplastic polymer blend containing
  • a polyphenylene ether P3 optionally as a compound together with a foamable polystyrene, wherein the component P2 to more than 4.5 wt .-%, based on the sum of P1, P2 and P3 is included.
  • the invention furthermore relates to polymer granules which are obtainable from the polymer blends according to the invention and to the use of the corresponding polymer granules for the production of particle foams and particle foam moldings.
  • Particulate foam moldings according to the invention have high solvent resistance, good temperature resistance, high mechanical rigidity, good propellant retention and good processability.
  • more than 4.5% by weight P2 are contained in the polymer blend based on the sum of P1, P2 and P3.
  • P1, P2 and P3 are contained in the polymer blend based on the sum of P1, P2 and P3:
  • polystyrene P1 radically polymerized glassy polystyrene (GPPS), impact modified polystyrene (HIPS), anionically polymerized polystyrene (A-PS) or, for example, anionic polymerized impact polystyrene (A-IPS) can be used.
  • GPPS radically polymerized glassy polystyrene
  • HIPS impact modified polystyrene
  • A-PS anionically polymerized polystyrene
  • A-IPS anionic polymerized impact polystyrene
  • GPPS or an impact-modified polystyrene (HIPS) or a mixture of GPPS and HIPS can be used.
  • HIPS impact-modified polystyrene
  • the elastic block copolymer P2 preferably contains at least one copolymerized units of a vinylaromatic monomer-containing, hard phase-forming block A and / or diene monomer-forming block B and at least one polymerized unit forming rubber-elastic (soft) phase a vinyl aromatic monomer and a diene-containing elastomeric, forming a soft phase block B / A, wherein the glass transition temperature Tg of the block A is above 25 0 C and that of the blocks B and B / A below 25 0 C and the phase volume ratio of block A to block B / A is selected so that the proportion of the hard phase in the total block copolymer 1-40% by volume and the proportion by weight of the diene is less than 50 wt .-%.
  • Suitable block copolymers are, for. As described in WO-A-95/35335.
  • Such a rubber-elastic block copolymer is obtained by forming, within the above parameters, the soft phase from a random copolymer of a vinyl aromatic with a diene;
  • Statistical Copolymerisa- te of vinyl aromatics and dienes is obtained by polymerization in the presence of a polar cosolvent.
  • a preferred block copolymer may, for. B. represented by one of the general formulas 1 to 11:
  • B / A stands for the soft phase, ie the block statistically composed of diene and vinylaromatic units
  • X is the residue of an n-functional initiator
  • Y is the residue of an m-functional coupling agent
  • n and n mean natural numbers from 1 to 10.
  • a block copolymer of one of the general formulas AB / AA, X - [- B / A - A] 2 and Y - [- B / AA] 2 meaning the abbreviations as above
  • a block copolymer comprising several blocks B / A and / or A of different molecular weights per molecule is also preferred.
  • a block B may be replaced by a block A, which is made up exclusively of vinylaromatic units, since, overall, all that matters is that a rubber-elastic block copolymer is formed.
  • Such copolymers may, for. Have the structure (15) to (18) (15) B- (B / A); (16) (B / A) -B- (B / A); (17) (B / A) 1-B- (B / A) 2; (18) B- (B / A) 1- (B / A). 2
  • Preferred as a vinyl aromatic compound in the context of the invention are styrene and also ⁇ -methylstyrene and vinyltoluene and mixtures of these compounds.
  • Preferred dienes are butadiene and isoprene, furthermore piperylene, 1-phenylbutadiene and mixtures of these compounds.
  • a particularly preferred monomer combination is butadiene and styrene. All of the following weights and volumes refer to this combination; if the technical equivalents of styrene and butadiene are used, it may be necessary to convert the information accordingly.
  • the B / A block is built up from about 75-30% by weight of styrene and 25-70% by weight of butadiene. More preferably, a soft block has a butadiene content of between 35 and 70% and a styrene content of between 65 and 30%.
  • the proportion by weight of the diene in the entire block copolymer in the case of the monomer combination styrene / butadiene is 15-65% by weight, that of the vinylaromatic component corresponding to 85-35% by weight.
  • Particular preference is given to butadiene-styrene block copolymers having a monomer composition of 25-60% by weight of diene and 75-40% by weight of vinylaromatic compound.
  • the block copolymers are prepared by anionic polymerization in a nonpolar solvent with the addition of a polar cosolvent.
  • the solvents used are preferably aliphatic hydrocarbons such as cyclohexane or methylcyclohexane.
  • polar aprotic compounds such as ethers and tertiary amines are preferred.
  • particularly effective ethers are tetrahydrofuran and aliphatic polyethers such as diethylene glycol dimethyl ether.
  • tert. Amines are tributylamine and pyridine.
  • the polar cosolvent is added to the nonpolar solvent in a small amount, e.g. B. from 0.5 to 5 vol% added.
  • Tetrahydrofuran is particularly preferred in an amount of 0.1-0.3% by volume. Experience has shown that in most cases an amount of about 0.2% by volume is sufficient.
  • the dosage and structure of the Lewis base determine the copolymerization parameters and the proportion of 1, 2 or 1, 4 linkages of the diene units.
  • the polymers have z. Example, a proportion of 15-40% of 1, 2-linkages and 85 - 60% of 1, 4-linkages based on all diene units.
  • the anionic polymerization is preferably initiated by means of organometallic compounds.
  • organometallic compounds Preference is given to compounds of the alkali metals, in particular of lithium.
  • initiators are methyllithium, ethyllithium, propyllithium, n-butyllithium, sec. Butyllithium and tert. Butyl lithium.
  • the organometallic compound is added as a solution in a chemically inert (inert) hydrocarbon. The dosage depends on the desired molecular weight of the polymer, but is usually in the range of 0.002 to 5 mol%, based on the monomers.
  • the polymerization temperature can be between 0 0 C and 130 0 C.
  • the temperature range is preferably between 30 ° C. and 100 ° C.
  • the volume fraction of the soft phase in the solid is of crucial importance.
  • the volume fraction of the soft phase built up from diene and vinylaromatic sequences is 60-95, preferably 70-90 and particularly preferably 80-90% by volume.
  • the blocks A formed from the vinylaromatic monomers form the hard phase, the volume fraction corresponding to 5-40, preferably 10-30 and particularly preferably 10-20% by volume.
  • the volume fraction of the two phases can be measured by contrasted electron microscopy or solid-state NMR spectroscopy.
  • the proportion of vinyl aromatic blocks can be determined after osmium degradation of the polydiene fraction by precipitation and precipitation.
  • the future phase ratio of a polymer can also be calculated from the monomer amounts used, if it is allowed to fully polymerize each time.
  • the block copolymer is uniquely defined by the quotient of the volume fraction in percent of the soft phase formed from the B / A blocks and the proportion of diene units in the soft phase which is between 25 and 70% by weight for the combination styrene / butadiene. % lies.
  • Tg glass transition temperature
  • the molecular weight of the block A is i. a. between 1000 to 200,000, preferably between 3,000 and 80,000 [g / mol]. Within a molecule, A blocks can have different molecular weights.
  • the molecular weight of the block B / A is usually between 2,000 and 250,000 [g / mol], preferably between 5,000 and 150,000 [g / mol].
  • block B / A can also assume different molecular weight values within a molecule.
  • Preferred polymer structures are AB / AA, X - [- B / AA] 2 and Y - [- B / AA] 2, where the random block B / A itself is again divided into blocks B1 / A1-B2 / A2-B3 / A3- ... can be divided.
  • the statistical block preferably consists of 2 to 15 statistical sub-blocks, more preferably 3 to 10 sub-blocks.
  • the division of the statistical block B / A into as many sub-blocks Bn / An offers the decisive advantage that even in the case of a composition gradient within a sub-block Bn / An, which is difficult to avoid under practical conditions in anionic polymerization.
  • the overall B / A block behaves like a nearly perfect random polymer. It is therefore advisable to add less than the theoretical amount of Lewis base, which increases the proportion of 1, 4-diene linkages, lowers the glass transition temperature Tg and reduces the tendency of the polymer to cure.
  • a larger or a smaller proportion of the sub-blocks can be equipped with a high diene content.
  • the diene occupies a weight fraction of 25% to 70% relative to the total mass, including vinylaromatic compound.
  • block A can be polymerized by adding the vinyl aromatic. Instead, required polymer blocks can also be linked together by the coupling reaction. In the case of bifunctional initiation, the B / A block is first established followed by the A block.
  • the polyphenylene ethers P3 used generally have a molecular weight (weight average M w ) in the range from 10,000 to 80,000 g / mol, preferably from 20,000 to 60,000 g / mol. This corresponds to a reduced specific viscosity (i "
  • a particularly suitable material system is the product Noryl 8890C marketed by GE Plastics (SABIC).
  • Particularly preferred polyphenylene ethers have recurring units of the formula
  • Ar is an aryl radical
  • R 1, R 2 , R 3 and R 4 are each independently monovalent substituents, in particular hydrogen, halide, in particular chlorine and bromine, alkyl, in particular straight-chain alkyl groups having 1 to 18 C atoms, for example methyl, ethyl, lauryl, stearyl; Alkoxy, in particular methoxy and ethoxy
  • Suitable polyphenylene ethers are preferably prepared by oxidative coupling of o-position disubstituted phenols.
  • substituents are halogen atoms such as chlorine or bromine and alkyl radicals having 1 to 4 carbon atoms, which preferably do not have an alpha-terminal tertiary hydrogen atom, for.
  • halogen atoms such as chlorine or bromine
  • alkyl radicals having 1 to 4 carbon atoms which preferably do not have an alpha-terminal tertiary hydrogen atom, for.
  • the alkyl radicals may in turn be substituted by halogen atoms such as chlorine or bromine or by a hydroxyl group.
  • substituents are alkoxy radicals, preferably having up to 4 carbon atoms or phenyl radicals optionally substituted by halogen atoms and / or alkyl groups. Also suitable are copolymers of various phenols such. B. Copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol. Of course, mixtures of different polyphenylene ethers can be used.
  • polyphenylene ethers are used which are compatible with vinyl aromatic polymers, i. H. wholly or largely soluble in these polymers (see A. Noshay, Block Copolymers, pp. 8-10, Academic Press, 1977 and O. Olabisi, Polymer-Polymer Miscibility, 1979, p.117-189).
  • polyphenylene ethers examples include poly (2,6-dilauryl-1,4-phenylene ether), poly (2,6-diphenyl-1,4-phenylene ether), P o I y (2, 6-dimethoxy-1, 4-phenylene ether ), Poly (2,6-diethoxy-1,4-phenylene ether), poly (2-methoxy-6-ethoxy-1,4-phenylene ether), poly (2-ethyl-6-stearyloxy-1,4-phenylene ether) , Poly (2,6-di-chloro-1, 4-phenylene ether), poly (2-methyl-6-phenyl-1, 4-phenylene ether, poly (2,6-dibenzyl-1, 4-phenylene) ether , Poly (2-ethoxy-1,4-phenylene ether), poly (2-chloro-1,4-phenylene ether), poly (2,5-dibromo-1,4-phenylene ether).
  • Polyphenylene ethers are preferably used in which the substituents are alkyl radicals having 1 to 4 carbon atoms, such as poly (2,6-dimethyl-1, 4-phenylene ether), poly (2,6-diethyl-1,4-phenylene ether), poly (2-methyl-6 -ethyl-1, 4-phenylene ether), poly (2-methyl-6-propyl-1,4-phenylene ether), poly (2,6-di-propyl-1,4-phenylene ether) and poly (2-ethyl- 6-propyl-1,4-phenylene ether).
  • the substituents are alkyl radicals having 1 to 4 carbon atoms, such as poly (2,6-dimethyl-1, 4-phenylene ether), poly (2,6-diethyl-1,4-phenylene ether), poly (2-methyl-6 -ethyl-1, 4-phenylene ether), poly (2-methyl-6-propyl-1,4-phenylene ether), poly (2,
  • copolymers can be prepared by the reaction of two or more different phenols.
  • PPE copolymers can be prepared from any of the above polyphenylene ethers by the addition of trialkylphenols such as 2,3,6-trimethylphenol.
  • graft copolymers of polyphenylene ether and vinylaromatic polymers such as styrene, ⁇ -methylstyrene, vinyltoluene and chlorostyrene are suitable.
  • polymer P4 In addition to the polymers P1 and P2, it is also possible for at least one polymer P4 different from P1 and P2 to be present.
  • polymer P4 z Acrylonitrile-styrene-acrylic esters (ASA), polyamide (PA), polyolefins such as polypropylene (PP) or polyethylenes (PE), polyacrylates such as polymethyl methacrylate (PMMA), polycarbonate (PC), polyesters such as polyethylene terephthalate (PET ) or polybutylene terephthalate (PBT), lyethersulfone (PES), polyether ketones (PEK) or polyether sulfides (PES) or mixtures thereof.
  • ASA Acrylonitrile-styrene-acrylic esters
  • PA polyamide
  • PA polyolefins
  • PP polypropylene
  • PE polyethylenes
  • PMMA polymethyl methacrylate
  • PC polycarbonate
  • PET polyethylene terephthalate
  • the polymer blend contains one or more blowing agents in a homogeneous distribution in a proportion of 2 to 12 wt .-%, preferably 3 to 9 wt .-%, based on the blowing agent-containing 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, esters or halogenated hydrocarbons. Preference is given to using isobutane, n-butane, isopentane, n-pentane. Ethane, acetone, methylal (dimethoxymethane) and methyl formate are preferred as co-propellants.
  • the invention further relates to a process for the preparation of polymer blends by a) mixing the components P1, P2 and P3 b) melting, preferably in an extruder c) degassing d) optionally mixing in a blowing agent and optionally additives e) cooling f) discharge through a G. Granulating, preferably through a 0.65 mm perforated plate in an underwater bath at 10-15 bar underwater pressure.
  • 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 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.
  • the pressurized underwater granulation, granulation with rotating knives and cooling by spray misting of tempering liquids or sputtering granulation are suitable for the granulation.
  • suitable apparatus arrangements are for. B .:
  • the propellant-containing 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 propellant-containing polymer melt.
  • the temperature of the nozzle plate is in the range of 20 to 100 0 C above the temperature of the propellant-containing polymer 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.
  • D diameter of the nozzle bores at the nozzle exit
  • the strand expansion can be influenced by the geometry of the die, apart from the molecular weight distribution.
  • 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 L / D is in the range of 3 to 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 exit diameter (D). The various embodiments of the nozzle geometry can also be combined.
  • the finished expandable polymer granules can be coated by glycerol esters, antistatic agents or anticaking agents.
  • finely divided internal water droplets can be introduced into the polymer matrix. This can be done for example by the addition of water in the molten 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.
  • Inner water droplets with a diameter in the range of 0.5 to 15 microns form during foaming foams with sufficient cell count and homogeneous foam structure.
  • the added amount of blowing agent and water is chosen so that the expandable polymer granules have an expansion capacity ⁇ , defined as bulk density before foaming / bulk density, after foaming at most 125, preferably 25 to 100.
  • the expandable polymer granules according to the invention generally have one
  • bulk densities in the range of 590 to 1200 g / l may occur.
  • the polymer melt may contain additives, nucleating agents, fillers, plasticizers, flame retardants, 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.
  • additives 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 eg. B organosilanes, epoxy group-containing polymers or maleic anhydride grafted styrene polymers to use.
  • Preferred plasticizers are mineral oils, low molecular weight styrene polymers, phthalates, which can be used in amounts of 0.05 to 10 wt .-%, based on the styrene polymer.
  • the expandable, thermoplastic polymer granules according to the invention are prefoamed in a first step preferably by means of hot air or steam to foam particles having a density in the range of 10 to 250 g / l and in a second step in a closed mold welded to the particle foam moldings according to the invention.
  • Component A Polyphenylene Ether Noryl 8890C (GE Plastics)
  • Component B1 Impact-modified polystyrene (HIPS) 486 M (BASF SE),
  • Component C elastic block copolymer based on butadiene / styrene
  • the melt was extruded through a heated perforated plate (4 holes with 0.65 mm bore and 280 ° C. perforated plate temperature).
  • the melt was extruded through a heated perforated plate (4 holes with 0.65 mm bore and 280 ° C. perforated plate temperature).
  • the melt was extruded through a heated perforated plate (4 holes with 0.65 mm bore and 280 ° C. perforated plate temperature).
  • component C In a twin-screw extruder from Leistritz ZSK 18, 20.6% by weight of component C were mixed with 72.0% by weight of polystyrene batch, 3.9% by weight of component A and 68.1% by weight of component B2 at 220 ° C. - 240 0 C melted. Subsequently, the polymer melt was loaded with 5.6 wt .-% pentane S, based on the polymer matrix. Thereafter, the polymer melt was homogenized in two static mixers and cooled to 180 0 C.
  • foams were produced as described below: By prefoaming the particle granules at densities of from 35 to 20 g / l at a pressure of 0.1 bar and, after 12-24 hours of intermediate storage time at a pressure of 1.0 bar, in the automatic molding machine, they were filled with foam into test plates.
  • the foams obtained in this way have the following properties:

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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)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP09781151A 2008-07-29 2009-07-28 Expandierbares thermoplastisches polymerblend Withdrawn EP2307497A1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP09781151A EP2307497A1 (de) 2008-07-29 2009-07-28 Expandierbares thermoplastisches polymerblend

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP08161337 2008-07-29
EP09781151A EP2307497A1 (de) 2008-07-29 2009-07-28 Expandierbares thermoplastisches polymerblend
PCT/EP2009/059697 WO2010012702A1 (de) 2008-07-29 2009-07-28 Expandierbares thermoplastisches polymerblend

Publications (1)

Publication Number Publication Date
EP2307497A1 true EP2307497A1 (de) 2011-04-13

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EP09781151A Withdrawn EP2307497A1 (de) 2008-07-29 2009-07-28 Expandierbares thermoplastisches polymerblend

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EP (1) EP2307497A1 (zh)
JP (1) JP5726735B2 (zh)
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Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK2384354T3 (da) 2008-12-30 2013-05-13 Basf Se Elastisk partikelskumplast på basis af polyolefin/styrenpolymerblandinger
KR101353631B1 (ko) 2009-03-05 2014-02-18 바스프 에스이 폴리올레핀/스티렌 중합체 혼합물을 기재로 하는 탄성 입자 발포체 물질
US8636929B2 (en) 2010-05-21 2014-01-28 Basf Se Nanoporous foamed active compound-containing preparations based on pharmaceutically acceptable thermoplastically workable polymers
JP2012172015A (ja) * 2011-02-18 2012-09-10 Sekisui Plastics Co Ltd 発泡性樹脂粒子及び発泡成形体

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0305862A1 (en) * 1987-09-04 1989-03-08 General Electric Company One-step process for the production of expandable foam beads
JP3486744B2 (ja) * 1997-05-29 2004-01-13 積水化成品工業株式会社 熱成形用発泡スチレン系樹脂積層シートとその製造方法及び成形品
US5889069A (en) * 1997-07-15 1999-03-30 The Dow Chemical Company High temperature syndiotactic styrene polymer foam
JP2000248099A (ja) * 1999-03-02 2000-09-12 Nippon Zeon Co Ltd 発泡成形用スチレン樹脂組成物
DE19910339A1 (de) * 1999-03-09 2000-09-14 Basf Ag Schlagzäh modifizierte Styrol/Diphenylethen-Copolymere
US20040209968A1 (en) * 2001-05-07 2004-10-21 Jos Bastiaens Flame retardant expandable poly(arylene ether)/polystyrene compositions and preparation thereof
US6583205B2 (en) * 2001-05-07 2003-06-24 General Electric Company Flame retardant expandable poly(arylene ether)/polystyrene compositions and preparation thereof
JP2003012847A (ja) * 2001-06-27 2003-01-15 Sumitomo Chem Co Ltd ポリフェニレンエーテル系樹脂組成物からなる発泡体
JP4156331B2 (ja) * 2002-10-04 2008-09-24 株式会社カネカ 熱可塑性樹脂発泡体およびその製造方法
ATE415455T1 (de) * 2003-09-30 2008-12-15 Asahi Kasei Chemicals Corp Verfahren zur herstellung einer polyphenylenetherharzzusammensetzung
KR101578953B1 (ko) * 2007-11-21 2015-12-18 바스프 에스이 난연성 팽창성 스티렌 중합체 및 이의 제조 방법

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2010012702A1 *

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