EP1723196A1 - Procede de production de plaques de mousse renfermant une charge - Google Patents

Procede de production de plaques de mousse renfermant une charge

Info

Publication number
EP1723196A1
EP1723196A1 EP05707420A EP05707420A EP1723196A1 EP 1723196 A1 EP1723196 A1 EP 1723196A1 EP 05707420 A EP05707420 A EP 05707420A EP 05707420 A EP05707420 A EP 05707420A EP 1723196 A1 EP1723196 A1 EP 1723196A1
Authority
EP
European Patent Office
Prior art keywords
polymer
filler
styrene
melt
foam
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Withdrawn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
EP05707420A
Other languages
German (de)
English (en)
Inventor
Dietrich Scherzer
Rüdiger BLUHM
Franz-Josef Dietzen
Swen RÜCK
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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 SE filed Critical BASF SE
Publication of EP1723196A1 publication Critical patent/EP1723196A1/fr
Withdrawn legal-status Critical Current

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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
    • C08J9/0066—Use of inorganic compounding ingredients
    • 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
    • C08J9/0085—Use of fibrous compounding ingredients
    • 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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/038—Use of an inorganic compound to impregnate, bind or coat a foam, e.g. waterglass
    • 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
    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/02—Condensation polymers of aldehydes or ketones only
    • 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
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/06—Polysulfones; Polyethersulfones

Definitions

  • the invention relates to a process for producing foam webs or sheets based on a polymer selected from polysulfones, polyetherimides, polyether ketones and styrene polymers, by extrusion of a melt which contains the polymer and a blowing agent, and subsequent foaming of this melt,
  • melt also contains 1 to 50% by weight, based on the polymer, of a filler selected from
  • the invention also relates to the foam webs or sheets obtainable by the process.
  • Foams made of polymers are obtained, for example, by foaming particles containing blowing agents.
  • EPS expandable polystyrene
  • styrene is polymerized in suspension with the use of a blowing agent, so that polystyrene particles containing blowing agent are obtained.
  • EPS expandable polystyrene
  • polystyrene particles containing blowing agent are obtained.
  • These can be foamed into the finished foam (particle foam) by treating them in closed molds with water vapor, causing the particles to expand and weld together.
  • the polymer In the extrusion process for the production of EPS, the polymer is provided with a nucleating agent - it enables foaming and causes a fine-cell foam to form when the polymer containing blowing agent expands - and then mixed in an extruder with melting, with a blowing agent which is fed to the extruder , The melt containing blowing agent is pressed out and granulated by means of an underwater pelletizer operated under excess pressure so that it does not foam. The resulting blowing agent-containing granulate is expanded into a particle foam.
  • the foam can also be produced directly using the extrusion process, for example XPS (expanded polystyrene).
  • XPS expanded polystyrene
  • the blowing agent-containing melt is produced in the extruder as described, but is pressed out directly into the free atmosphere.
  • the melt strand foams to the finished foam, whereby it is usually formed directly into a foam sheet, which is then cut into sheets.
  • EP-A 1 002 829 describes the production of particulate, expandable styrene polymers (EPS) in suspension and in the presence of 1 to 25% by weight of graphite particles, glass fibers, silicates, metal pigments or metal oxides as a solid.
  • EPS particulate, expandable styrene polymers
  • particle foam molded parts which are obtained by welding pre-expanded foam particles made of expandable, filler-containing polymer granules.
  • the polymers used include Styrene polymers, polyether sulfones and polyether ketones, and as fillers, etc. Silicates, glass balls, zeolites, metal oxides, carbonates, hydroxides, sulfates, and glass fibers in amounts of 1 to 50% by weight.
  • the production of the expandable granules by extrusion with a blowing agent and underwater granulation is also described.
  • DE-A 4207 057 describes a process for foaming high-melting aromatic plastics, e.g. Polyetherimides, polyether sulfones, etc. to form foam webs by the extrusion process, the melt having to be cooled in a certain way in the extruder before foaming. Fillers are not mentioned.
  • aromatic plastics e.g. Polyetherimides, polyether sulfones, etc.
  • EP-A 1 333 051 discloses a method for producing foam webs from a polysulfone or a polyethersulfone by extrusion with a blowing agent and extrusion into the free atmosphere. Fillers are not mentioned.
  • WO 03/018678 shows a process for the production of open-cell foam sheets by extrusion of a styrene polymer melt with a blowing agent. Only carbon particles, e.g. Graphite, in amounts of 1 to 10 wt .-% based on the styrene polymer mentioned.
  • carbon particles e.g. Graphite
  • the older, not prepublished application DE Az. 10307736.7 describes a foam made of a high-temperature-resistant plastic (including polyetherimides, polysulfones, polyether ketones) by extrusion with a blowing agent and squeezing into the free atmosphere.
  • a foam made of a high-temperature-resistant plastic including polyetherimides, polysulfones, polyether ketones
  • the desired open-cell nature of the foam can be achieved, inter alia, by adding powdery solids in amounts of 0.1 to 5% by weight, based on the polymer mass. Only graphite or graphite together with talc or other solids are mentioned as powdery solids.
  • the compressive strength of the foam is of crucial importance for certain applications of foam panels, for example for perimeter insulation (insulation in contact with the ground, eg on the outside of the basement) or if the insulated area should be accessible (eg inverted roofs, ie roofs with external insulation). Adequate pressure resistance is also desirable for high-temperature-resistant foams that have to be pressure-resistant because the insulation also serves as protection against mechanical influences or as a housing.
  • Such applications are, for example, insulating panels or molded parts obtainable therefrom as insulation or housings for motors, other machines or pipes for hot media.
  • fire behavior of the known foams is not optimal.
  • fire and smoke gases of high density can develop under unfavorable conditions.
  • high density means that the flue gas contains many suspended matter (solid or liquid particles) per unit volume.
  • low-density smoke gases would be advantageous.
  • the foam sheets should show improved fire behavior.
  • the smoke gases produced should have a lower density (fewer suspended matter per unit volume).
  • the plates should have both properties, i.e. an improved compressive strength and smoke gases with lower density.
  • the foam webs or sheets are produced from a polymer which is selected from polysulfones, polyetherimides, polyether ketones and styrene polymers.
  • Suitable polysulfones are all polymers whose repeat units are linked by sulfone groups -SO2-, in particular polymers of the following general formulas 1 to 4:
  • R ' is alkyl or aryl, R aryl, in particular phenyl, and n is the number of repeat units.
  • Formula 2 represents the actual polysulfone (PSU).
  • the suitable polysulfones include in particular the polyarylsulfones, polyphenylene sulfones (PPSU), polyether sulfones (PES) and polyaryl ether sulfones.
  • PPSU polyphenylene sulfones
  • PES polyether sulfones
  • Formulas 3 and 4 illustrate polyaryl ether sulfones. All of these polysulfones are suitable.
  • the softening temperatures of the polysulfones are usually around 180 to 230 ° C.
  • Suitable polysulfones are known and commercially available, for example as polysulfone Ultrason® S from BASF, or the polyether sulfone Ultrason® E from BASF
  • Suitable polyetherimides are polymers whose main chains consist of ether groups and imide groups
  • linked aromatic rings are constructed, for example those of the form in 5 or 6
  • the softening temperatures of the polyetherimides are generally about 200 to 230 ° C.
  • Suitable polyetherimides are known and commercially available, for example as Ultem® from GE Plastics or Vespel® from DuPont.
  • polyaryl ether ketones PAEK
  • PEEK polyaryl ether ketones
  • the softening temperatures of the polyether ketones are usually around 210 to 350 ° C.
  • Suitable polyether ketones are known and commercially available, for example as Ultrapek® from BASF.
  • Polymers of styrene compounds are suitable as styrene polymers, for example styrene, ⁇ -methylstyrene, p-methylstyrene, ethylstyrene, tert-butylstyrene, vinylstyrene, vinyltoluene, 1, 2-diphenylethylene, 1,1-diphenylethylene or mixtures thereof.
  • Styrene is particularly preferably used.
  • the styrene polymers can be homopolymers, for example (rubber-free) polystyrene (GPPS, general purpose polystyrene), or copolymers.
  • Suitable comonomers which are contained in these copolymers are, for example, nitrile compounds such as acrylonitrile or methacrylonitrile; Dienes like 1,3-butadiene (short: butadiene), 1,3-pentadiene, 1,3- Hexadiene, 2,3-dimethylbutadiene, isoprene or piperylene; Acrylates, in particular C ⁇ _ 12 - alkyl acrylates such as n- or tert-butyl acrylate or 2-ethylhexyl acrylate, and the corresponding methacrylates, such as methyl methacrylate (MMA).
  • MMA methyl methacrylate
  • Particularly suitable comonomers are acrylonitrile, butadiene and n-butyl acrylate.
  • a preferred styrene copolymer is impact-resistant polystyrene (HIPS, high impact polystyrene). It usually contains a butadiene rubber as the rubber phase, which is contained in a styrene polymer hard matrix, e.g. Polystyrene, is dispersed.
  • the butadiene rubber can be, for example, polybutadiene or a styrene-butadiene block copolymer, the latter e.g.
  • S-B styrene block
  • B butadiene block
  • Styrene-butadiene block copolymers are also as such, i.e. without a styrene hard matrix, suitable as a styrene copolymer.
  • styrene copolymer is styrene-acrylonitrile copolymer (SAN).
  • SAN styrene-acrylonitrile copolymer
  • the acrylonitrile content is usually 5 to 50, preferably 10 to 40 and particularly preferably 20 to 35% by weight, based on the SAN.
  • ABS Acrylonitrile-butadiene-styrene copolymer
  • ABS Acrylonitrile-styrene-acrylic ester copolymer
  • D acrylonitrile-EP M-styrene copolymer
  • Preferred ABS copolymers contain a butadiene rubber, preferably polybutadiene, as the rubber phase, dispersed in a hard matrix made of styrene-acrylonitrile copolymer. The rubber is usually grafted with styrene and acrylonitrile in order to improve the binding of the rubber phase to the hard matrix.
  • ASA and AES are constructed analogously; Instead of the butadiene rubber, ASA contains an acrylic ester rubber, for example made of n-butyl acrylate. AES uses a rubber made of EPM (ethylene propylene monomer) or EPDM (ethylene propylene diene monomer).
  • EPM ethylene propylene monomer
  • EPDM ethylene propylene diene monomer
  • the styrene polymers are selected from rubber-free polystyrene, impact-resistant polystyrene, styrene-acrylonitrile copolymer (SAN), acrylonitrile-butadiene-styrene copolymer (ABS) and acrylonitrile-styrene-acrylic ester copolymer (ASA).
  • styrene polymers are known and commercially available, for example as Polystyrol®, Luran® (SAN), Terluran® (ABS) or Luran® S (ASA), all from BASF.
  • SAN Luran®
  • ABS Terluran®
  • ASA Luran® S
  • blowing agents such as carbon dioxide (CO 2 ), nitrogen or argon are suitable as blowing agents; Water; aliphatic C 3 -C 6 hydrocarbons, such as propane, butane, pen tan or hexane (all isomers, eg n- or iso-); aliphatic alcohols or aliphatic ketones with a boiling point between 56 and 100 ° C., for example methanol, ethanol, propanol, isoproanol, butanol, acetone or methyl ethyl ketone (2-butanone); aliphatic esters such as methyl or ethyl acetate; halogenated, in particular fluorinated hydrocarbons such as 1,1,1,2-tetrafluoroethane (R 134a) or 1,1-difluoroethane (R 152a); or chemical blowing agents, for example azo or diazo compounds, which release gases when heated. In many cases, blowing agent mixtures
  • Halogen-free blowing agents in particular water, CO 2 , isobutane, acetone and ethanol, are particularly preferably used. It is very particularly preferred to use a blowing agent mixture of water and acetone for plates based on polysulfones, polyetherimides or polyether ketones, and a mixture of water and CO 2> for plates based on styrene polymers.
  • One advantage of using mixtures of water and another blowing agent is that highly flammable liquids at high temperatures, such as those required to foam the polysulfones, polyetherimides or polyether ketones, are only used in small quantities, thus reducing the safety risk ,
  • the amount of blowing agent depends on the desired density of the foam sheets.
  • the blowing agent is added to the polymer melt in amounts of 0.1 to 15% by weight, preferably in amounts of 3 to 12% by weight, based on the polymer and calculated as the sum of all blowing agents.
  • nucleating agent can also be used to control the cell number of the foam.
  • Nucleating agents create a large number of pores at the start of the foaming process and contribute to a fine and uniform pore structure.
  • a large number of additives can serve as nucleating agents, for example finely divided solids which are infusible under the process conditions, such as silica gel, talc, chalk, layered silicates, metal carbonates and hydrogen carbonates, carbon black, graphite, boron nitride, azo compounds, silicas such as Aerosil® from Degussa, Aluminum nitride, aluminum silicates, calcium sulfate, mica, nanoparticles from eg Glass, and wollastonite.
  • nucleating agents for example finely divided solids which are infusible under the process conditions, such as silica gel, talc, chalk, layered silicates, metal carbonates and hydrogen carbonates, carbon black, graphite, boron nitride, azo compounds, silicas such as Aerosil® from Degussa, Aluminum nitride, aluminum silicates, calcium sulfate, mica, nanoparticles from eg Glass, and wol
  • Solid additives which serve as flame retardants to improve fire resistance can also act as nucleating agents, as can the inert gases such as nitrogen or noble gases already mentioned.
  • the latter can be mixed into the polymer melt under high pressure (eg 60 to 250 bar absolute).
  • nucleating agents are chemical blowing agents (preferably in small amounts) such as sodium hydrogen carbonate and citric acid, commercially available, for example as Hydrocerol® CF from Clariant. If a nucleating agent is used, the amount is usually 0.01 to 2% by weight, based on the polymer.
  • the melt contains 1 to 50% by weight, based on the polymer, of a filler which is selected from a fibrous filler A, a particulate filler B different from graphite, and mixtures of the fillers A and B.
  • Suitable fibers A are all fibers which do not melt at the temperatures prevailing in the polymer melt.
  • Organic fibers are suitable, e.g. Fibers made from flax, hemp, ramie, jute, sisal, cotton, cellulose or aramid, and - preferably - inorganic fibers, in particular carbon fibers, glass fibers and fibrous silicates such as wollastonite or asbestos.
  • glass fibers as fibrous filler A is particularly preferred. You can e.g. as short glass fibers, or also in the form of glass fabrics, glass mats or glass silk rovings (endless strands). If necessary, the glass fabrics, mats or rovings are cut before they are mixed into the polymer melt. Using cut glass is also possible.
  • the fibrous fillers in particular the glass fibers, can be provided with a size and / or an adhesion promoter for better compatibility with the polymer, or they can be hydrophobic.
  • the average fiber length of the fibrous filler A before mixing with the polymer is preferably 0.1 to 10 and in particular 1 to 4 mm.
  • the average fiber diameter of the fibrous filler A before mixing with the polymer is preferably 2 to 40, in particular 5 to 25 ⁇ m.
  • the ratio of average fiber length to average fiber diameter before mixing with the polymer is particularly preferably 5000: 1 to 4: 1, in particular 100: 1 to 10: 1.
  • the incorporation of the filler into the polymer can change the fiber lengths or diameters mentioned, which is why the lengths or diameters are given above before they are mixed with the polymer.
  • the shear forces occurring in the extruder can break up or agglomerate the filler. This also applies to the particulate filler B described below and its particle diameter.
  • the amount of fibrous filler A according to the invention is 1 to 50, preferably 2 to 40 and particularly preferably 5 to 20% by weight, based on the polymer used.
  • Suitable particles B are all particles which do not melt at the temperatures prevailing in the polymer melt.
  • the particles can e.g. be spherical or platelet-shaped, or have an irregular shape. They can be "massive” or have atomic or macroscopic internal cavities, e.g. zeolites or hollow spheres.
  • Suitable particulate fillers B are, for example, natural or synthetic calcium carbonates (e.g. chalk, dolomite); magnesium carbonates; Alkaline earth metal sulfates such as calcium sulfate or barium sulfate or heavy spar; Silicates such as glass balls or powder, talc or talc, kaolin, mica (mica, e.g. muscovite), feldspars such as nepeline, zeolites, bentonites, smectites, wollastonite, asbestos or other silicates of aluminum, calcium or magnesium; Quartz powder and natural and synthetic silicas or silica (silica), especially pyrogenic silicas such as e.g.
  • natural or synthetic calcium carbonates e.g. chalk, dolomite
  • magnesium carbonates e.g. chalk, dolomite
  • Alkaline earth metal sulfates such as calcium sulfate or barium sulfate or heavy spar
  • Silicates such
  • Aerosil® from Degussa Metal oxides such as aluminum oxide (alumina) or zirconium oxide; Metal hydroxides such as aluminum hydroxide or magnesium hydroxide; Metal nitrides such as aluminum nitride; Metal flakes or flakes e.g. made of aluminum or bronze, silicon carbide; and aluminum diboride. According to the invention, graphite is excluded as a particulate filler.
  • the particulate filler B is preferably selected from calcium carbonate, calcium sulfate and talc.
  • the average particle diameter of the particulate filler B before mixing with the polymer is preferably 0.1 to 1000, particularly preferably 0.2 to 300 ⁇ m.
  • non-spherical particles e.g. Platelet
  • particle diameter the greatest linear expansion.
  • the aspect ratio (diameter of the platelet / thickness of the platelet) before mixing with the polymer is usually 1000: 1 to 1: 1, in particular 100: 1 to 2: 1.
  • the ratio is the greatest with this aspect ratio to mean the smallest linear expansion.
  • the amount of the particulate filler B according to the invention is 1 to 50, preferably 2 to 40 and particularly preferably 5 to 30% by weight, based on the polymer used.
  • Low-melting glass is also suitable as a filler.
  • This is, for example, an alkali-zinc-phosphate glass with a glass transition temperature of approx. 275 ° C, as is commercially available, for example, as Corning's Cortem TM.
  • the low-melting glass belongs to the fibrous fillers A or to the particulate fillers B.
  • the amount of filler A or B required in individual cases depends, among other things. according to the desired mechanical properties of the foam sheet, for example the desired compressive strength, and the fire behavior, e.g. the smoke density to be maintained in the event of a fire and can be determined by preliminary tests.
  • adhesion promoters such as styrene copolymers modified with maleic anhydride, polymers containing epoxy groups, organosilanes or styrene copolymers with isocyanate or acid groups can also be used. These adhesion promoters can improve the connection of the filler to the polymer matrix and thus the mechanical properties of the foam sheets.
  • customary additives can also be used in the amounts customary for these materials, e.g. Lubricants or mold release agents, colorants such as e.g. Pigments or dyes, flame retardants, antioxidants, light stabilizers or antistatic agents, as well as other additives, or mixtures thereof.
  • a melt is extruded which contains the polymer, the blowing agent and, according to the invention, the filler A and / or B.
  • the polymer is usually carried out as a solid, e.g. as granules or powder, to an extruder and the polymer is melted in the extruder, but it is also possible to prepare a polymer melt beforehand and feed it to the extruder.
  • the blowing agent is also metered into the extruder, usually under excess pressure. It is preferably metered into the polymer melt, but it can also be added to the solid polymer and the extruder melts the polymer. In any case, a largely homogeneous mixture of polymer and blowing agent is created.
  • the filler is fed to the extruder. It is mixed uniformly with the melt in the extruder, but is usually not melted, so that a melt containing blowing agent with filler fibers or particles dispersed therein is obtained receives.
  • the low-melting glass mentioned is used as a filler, the glass can become plastic or melt, depending on the extruder temperature, and the foam produced when such a melt is cooled and foamed can have, for example, a polymer phase and a glass phase which penetrate one another.
  • the filler can, for example, be fed as such directly to the extruder by metering it directly into the extruder, or a mixture (blend) can be prepared beforehand from the polymer and the filler, which is then added to the extruder.
  • a mixture blend
  • Certain such mixtures of polymer and filler are commercially available as so-called reinforced or filled polymer blends, and such a commercially available blend can be used if it has the desired filler content.
  • the desired filler content of the foam sheet can be adjusted by mixing appropriate proportions of two polymers or polymer blends, the first polymer containing less and the second polymer containing more filler than the desired foam sheet is to contain.
  • plates with a filler content of 10% by weight can be produced by mixing equal amounts of a filler-free polymer I and a polymer II containing 20% by weight of filler.
  • the polymers can be mixed in advance or only in the extruder, i.e. the two polymers are fed separately to the extruder, where they are mixed.
  • the process is characterized in that a mixture of two polymers I and II is used as the polymer, the polymer I containing no filler, and the polymer II the fibrous filler A, or the particulate filler B, or their Mixtures.
  • additives for example the nucleating agents, adhesion promoters or additives mentioned, are likewise fed to the extruder or are already contained in the polymer used.
  • extruders Conventional single- or twin-screw extruders can be used as extruders.
  • the temperatures, pressures and other operating conditions along the extruder are selected in such a way that, on the one hand, the polymer is melted and mixed uniformly with the blowing agent and the filler, and on the other hand, the melt at the end of the extruder is still so viscous that it subsequently seals Foaming forms a good foam.
  • the screw speed and geometry should be selected such that the filler fibers or particles are not broken up or only agglomerated or agglomerated to the desired extent by the resulting shear forces. This applies in particular to fibrous fillers A; whose fiber length usually decreases from a few mm before mixing to a few 100 // m in the polymer foam obtained.
  • a so-called tandem system is preferably used, which consists of two extruders.
  • the first, so-called melting extruder the polymer is first melted at a temperature above its softening temperature, the filler is metered in, and the blowing agent is pressed into the melt and mixed.
  • the second, so-called cooling extruder the mixture is cooled to a temperature at which the melt viscosity ensures a good foam.
  • the polymer melt containing blowing agent and filler is then foamed. This is done in the usual way by pressing the melt out of the extruder, ambient pressure and temperature outside the extruder being set such that the blowing agent expands and the melt foams while solidifying. Ambient pressure and temperature when foaming are known, among other things. according to the desired density of the foam sheets, the type of polymer and the type and amount of blowing agent. For example, you can squeeze and foam into the free atmosphere at room temperature (23 ° C).
  • an appropriately designed nozzle plate e.g. a slot die to which a so-called calibration device connects.
  • a foam sheet is immediately obtained, which is continuously pulled off.
  • the thickness and width of the web can be set by the calibration device, which is then cut into plates.
  • the thickness of the foam sheets obtained is usually 5 to 1000, in particular 10 to 500 mm, their width is generally 100 to 2000, preferably 200 to 1500 mm, and their cross-sectional area is usually 10 to 20,000, in particular 20 to 7500 cm 2 .
  • the foam sheets obtained preferably have a density of 15 to 200, particularly preferably 20 to 120 g / l, determined according to DI EN 826.
  • filler generally makes the foam sheet more fine-celled and open-celled.
  • blowing agent, foam density and process parameters allows the open-cell nature to be varied, and in most cases both open-cell and closed-cell foams can be produced from a given polymer.
  • the varied process parameters are, for example, temperature and pressure in the extruder and the geometry of the nozzle through which the extruder contents are pressed out.
  • the foam is closed-cell, ie there are discrete gas cells in the foam, and it has an open cell of at most 40, preferably at most 20 and particularly preferably a maximum of 10%, determined in accordance with DIN EN ISO 4590.
  • suitable process conditions can also be used to produce foams with a higher open cell content.
  • the cell size of the gas cells is generally 5 to 1000, preferably 50 to 500 ⁇ m, determined by measuring the cells under the light microscope.
  • the compressive strength of the panels naturally depends on the polymer used.
  • it is preferably 0.05 to 3, in particular 0.2 to 2 N / mm 2
  • plates made of styrene polymers preferably 0.1 to 2, in particular 0.15 to 1 N / mm 2 , determined according to ISO 844 at 23 ° C.
  • the invention also relates to the foam webs or sheets obtainable by the process according to the invention, in particular those which have a density of 15 to 200 g / l, determined in accordance with DIN EN 826.
  • the plates according to the invention can be used in many ways, e.g. as cores for sandwich elements, buoyancy bodies e.g. for watercraft and for sound or heat insulation of buildings, machines or vehicles.
  • the foam sheets obtained by the process according to the invention are notable for improved compressive strength.
  • their fire behavior is improved, in particular the smoke gases produced have a lower density, in each case compared to plates which are obtained by the methods of the prior art.
  • the method according to the invention is equally suitable for polymers as diverse as polysulfones, polyetherimides and polyether ketones, that is to say high-temperature-resistant plastics, and conventional styrene polymers.
  • PES a non-filler-containing polyethersulfone; the commercial product Ultrason® E 2010 from BASF was used,
  • PES-G a polyethersulfone containing 20% by weight of glass fibers with an average fiber length in the polymer of 200 ⁇ m and an average fiber diameter of 15 ⁇ m; the commercial product Ultrason® E 2010 G4 from BASF was used, SAN: a non-filler-containing styrene-acrylonitrile copolymer; the commercial product Luran® 378 P from BASF was used,
  • SAN-G a styrene-acrylonitrile copolymer containing 35% by weight of glass fibers with an average fiber length in the polymer of 200 ⁇ m and an average fiber diameter of 15 m; the commercial product Luran® 378 P G7 from BASF was used,
  • Chalk a natural calcium carbonate (98% of the particles ⁇ 3 ⁇ m, 82% ⁇ 1 ⁇ m); the commercial product Hydrocarb® OG from Omya was used,
  • Talc Talc with an average particle diameter D 50 of 1.5 ⁇ m; the commercial product Micro-Tale IT Extra from Mondo Minerals Oy was used.
  • a tandem system was used, which consisted of a melting extruder and a downstream cooling extruder.
  • the polymer or the polymer mixture (see table) was continuously fed to the melting extruder together with the nucleating agent talc or the filler chalk.
  • the blowing agents (water, acetone or CO 2 , see table) were fed in continuously through an inlet opening on the melting extruder.
  • the polymer melt containing blowing agent was cooled to the foaming temperature (see table) in the cooling extruder and extruded through a slot die.
  • the foaming melt was shaped in a calibration device into foam sheets of the thickness or width specified in the table.
  • the density of the plates according to DIN EN 826 and the compressive strength of the plates according to ISO 844 at 23 ° C were determined.
  • V means comparative example, TL. Parts and Acet. Acetone.
  • the amounts of the starting materials in% by weight relate to the polymer melt.
  • Foam sheets (it means V comparative example, partial parts, and acet. Acetone)
  • the examples show that the glass fiber-containing foam sheets made of PES (example 2) produced by the process according to the invention, compared with the filler-free PES sheets (example 1V) not according to the invention, had a significantly higher compressive strength with comparable density.
  • Even when chalk was used as the particulate filler the compressive strength of the PES plates was higher at a comparable density than for PES plates without chalk (Examples 6 and 5V).
  • the process was suitable for both PES and SAN, and for both fibrous and particulate fillers.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

L'invention concerne un procédé de production de bandes continues de mousse ou de plaques de mousse, à base d'un polymère sélectionné à partir de polysulfones, polyétherimides, polyéthercétones et styrolpolymères, par extrusion d'une masse fondue renfermant le polymère et un agent de gonflage, suivie d'un moussage de cette masse fondue. Le procédé est caractérisé en ce que la masse fondue renferme en outre 1 à 50 % en poids, par rapport au polymère, d'une charge sélectionnée à partir de A) une charge fibreuse A, B) une charge particulaire B, différente du graphite, et des mélanges de ces produits.
EP05707420A 2004-02-18 2005-02-16 Procede de production de plaques de mousse renfermant une charge Withdrawn EP1723196A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004008201A DE102004008201A1 (de) 2004-02-18 2004-02-18 Verfahren zur Herstellung füllstoffhaltiger Schaumstoffplatten
PCT/EP2005/001544 WO2005082984A1 (fr) 2004-02-18 2005-02-16 Procede de production de plaques de mousse renfermant une charge

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EP1723196A1 true EP1723196A1 (fr) 2006-11-22

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US (1) US20070164466A1 (fr)
EP (1) EP1723196A1 (fr)
JP (1) JP2007523243A (fr)
DE (1) DE102004008201A1 (fr)
WO (1) WO2005082984A1 (fr)

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WO2009016892A1 (fr) * 2007-08-01 2009-02-05 Techno Polymer Co., Ltd. Composition de résine thermoplastique pour le moulage par expansion, article moulé par expansion et article multicouches
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US20070164466A1 (en) 2007-07-19
JP2007523243A (ja) 2007-08-16
WO2005082984A1 (fr) 2005-09-09
DE102004008201A1 (de) 2005-09-01

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