DE3220856A1 - Process for the preparation of foams - Google Patents

Process for the preparation of foams

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Publication number
DE3220856A1
DE3220856A1 DE19823220856 DE3220856A DE3220856A1 DE 3220856 A1 DE3220856 A1 DE 3220856A1 DE 19823220856 DE19823220856 DE 19823220856 DE 3220856 A DE3220856 A DE 3220856A DE 3220856 A1 DE3220856 A1 DE 3220856A1
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Germany
Prior art keywords
foams
mixture
weight
pressure
plastic
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Withdrawn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
DE19823220856
Other languages
German (de)
Inventor
Franz Dr. Dipl.-Chem. 6730 Neustadt Brandstetter
Adolf Dr. Dipl.-Chem. 6700 Ludwigshafen Echte
Juergen Dr. Dipl.-Chem. 6903 Neckargemuend Hambrecht
Gerhard Dr. Dipl.-Chem. 6906 Leimen Lindenschmidt
Edmund Dr. Dipl.-Chem. 6710 Frankenthal Priebe
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BASF SE
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BASF SE
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Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to DE19823220856 priority Critical patent/DE3220856A1/en
Publication of DE3220856A1 publication Critical patent/DE3220856A1/en
Withdrawn legal-status Critical Current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
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
    • B29C44/3442—Mixing, kneading or conveying the foamable material
    • 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
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2371/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/04—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
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2471/12—Polyphenylene oxides

Landscapes

  • 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)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to a process for the preparation of foams by melting a thermoplastic, mixing the melt with a volatile blowing agent at a pressure of from 25 to 250 bar, decompressing the mixture to atmospheric pressure, and cooling the foam. The plastic used is a mixture of A) from 95 to 20% by weight of a styrene polymer and B) from 5 to 80% by weight of polyphenylene oxide. The resultant foams having high heat distortion resistance can be used as insulating materials.

Description

Verfahren zur Herstellung von SchaumstoffenProcess for the production of foams

Schaumstoffe aus Styrolpolymerisaten werden nach einem bekannten Verfahren hergestellt durch Aufschmelzen des Kunststoffs in einem Extruder, Vermischen mit einem flüchtigen Treibmittel unter Druck, Auspressen der Mischung an die Umgebungsatmosphäre und Abkühlen. Die Dichte solcher Schaumstoffe liegt im allgemeinen zwischen 25 und 50 g.7-1. Sie zeichnen sich durch ein gutes Wärmeisoliervermögen sowie durch eine verhältnismäßig hohe Druckfestigkeit aus, weisen Jedoch eine niedrige Wärmeformbeständigkeit auf.Foams made from styrene polymers are produced by a known method produced by melting the plastic in an extruder, mixing it with a volatile propellant under pressure, expelling the mixture to the ambient atmosphere and cooling down. The density of such foams is generally between 25 and 50 g.7-1. They are characterized by good thermal insulation properties and by a relatively high compressive strength, but have a low heat resistance on.

Man hat schon versucht, durch Verwendung von Copolymerisaten des Styrols, z.B. mit Maleinsäureanhydrid, Schaumstoffe mit höherer Wärmeformbeständigkeit herzustellen (s. BE-PS 705 163 und 721 152), jedoch reicht dies für viele Anwendungszwecke nicht aus.Attempts have already been made to use styrene copolymers, E.g. with maleic anhydride to produce foams with higher heat resistance (See BE-PS 705 163 and 721 152), but this is not enough for many applications the end.

Der Erfindung lag daher die Aufgabe zugrunde, Schaumstoffe mit erhöhter Wärmeformbeständigkeit durch Aufschmelzen eines thermoplastischen Kunststoffs, Vermischen mit einem flüchtigen Treibmittel bei einem Druck von 50 bis 250 bar, Entspannen der Mischung auf Atmosphärendruck und Abkühlen des Schaumstoffs herzustellen.The invention was therefore based on the object of providing foams with increased Heat resistance through melting a thermoplastic material, mixing with a volatile blowing agent at a pressure of 50 to 250 bar, decompression of the mixture to produce atmospheric pressure and cooling the foam.

Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß man als Kunststoff ein Gemisch verwendet aus A. 95 bis 20 Gew.-%, vorzugsweise 90 bis 50 Gew.-% eines Styrolpolymerisats und B. 5 bis 8 Gew.-%, vorzugsweise 10 bis 50 Gew.-% Polyphenylenoxid.According to the invention, this object is achieved in that the plastic a mixture used from A. 95 to 20 wt .-%, preferably 90 to 50 wt .-% of one Styrene polymer and B. 5 to 8% by weight, preferably 10 to 50% by weight, of polyphenylene oxide.

Es war zwar bekannt, daß Mischungen aus Polyphenylenoxid mit Styrolpolymerisaten, insbesondere mit kautschukhal- einem schlagzähem Polystyrol gute mechanische Eigenschaften und eine hohe Wärmeformbeständigkeit aufweisen. Wegen der stark unterschiedlichen Erweichungstemperaturen und Viskositätseigenschaften der beiden Kunststoffe sowie der unterschiedlichen Löslichkeit der Treibmittel in diesen Polymeren war jedoch nicht ohne weiteres zu erwarten, daß sich aus solchen Mischungen problemlos Schaumstoffe nach dem beschriebenen Verfahren herstellen lassen.It was known that mixtures of polyphenylene oxide with styrene polymers, especially with rubber an impact-resistant polystyrene good have mechanical properties and high heat resistance. Because the widely differing softening temperatures and viscosity properties of the two plastics and the different solubility of the propellants in however, these polymers were not readily expected to result from such Mixtures can easily produce foams by the method described.

Als Styrolpolymerisate kommen neben Polystyrol auch Mischpolymerisate des Styrols mit bis zu 50 Gew.-% an Comonomeren, z.B. «-Methylstyrol, Acrylnitril oder Ester der Acryl- oder Methacrylsäure in Frage, sowie mit Kautschuken schlagzäh modifiziertes Polystyrol.In addition to polystyrene, mixed polymers are also used as styrene polymers of styrene with up to 50% by weight of comonomers, e.g. methyl styrene, acrylonitrile or esters of acrylic or methacrylic acid in question, as well as impact-resistant with rubbers modified polystyrene.

Als Treibmittel eignen sich aliphatische Kohlenwasserstoffe, wie Butan, Pentan oder Hexan; insbesondere aber solche, die erst unter Druck im Polymeren löslich sind, wie Methylchlorid, Fluorchlorkohlenwasserstoffe oder Kohlendioxid. Auch Treibmittelgemische können verwendet werden.Aliphatic hydrocarbons such as butane, Pentane or hexane; but especially those that only dissolve in the polymer under pressure are, such as methyl chloride, chlorofluorocarbons or carbon dioxide. Also propellant mixtures can be used.

Die Trelbmittelmenge liegt zwischen 5 und 20 Gew.-%> vorzugsweise zwischen 8 und 15 Gew-%, bezogen auf den Kunststoff.The amount of dripping agent is between 5 and 20% by weight> preferably between 8 and 15% by weight, based on the plastic.

Die Schaumstoffe enthalten als Flaminschutzmittel vorzugsweise Halogenverbindungen, die bei hohen Temperaturen stabil sind, z.B. Hexabromcyclododecan, Pentabrommonochlorcyclohexan#und Chlorparaffine. Sie werden in Mengen von 0,5 bis 10 Gew.-%> vorzugsweIse von 1 bis 5 Gew.-%, bezogen auf den Kunststoff, eingesetzt.The foams preferably contain halogen compounds as flame retardants, which are stable at high temperatures, e.g. hexabromocyclododecane, pentabromomonochlorocyclohexane # and Chlorinated paraffins. They are preferably used in amounts of 0.5 to 10% by weight 1 to 5% by weight, based on the plastic, are used.

Ferner können übliche Zusatzstoffe, wie z.B. Stabilisatoren, Keimbildungsmittel zur Steuerung der Zellgröße> Farbstoffe, Füllstoffe oder auch Flammschutzsynergisten zugesetzt werden.Customary additives such as stabilizers, nucleating agents to control the cell size> dyes, fillers or flame retardant synergists can be added.

#ur Herstellung der Schaumstoffe wird die Mischung aus dem Styrolpolymerisat und Polyphenylenoxid aufgeschmolzen. In diese Schmelze wird dann vorzugsweise bei Temperaturen zwischen 200 und 25000 unter einem Druck von 25 bis 250 bar, vorzugsweise zwischen 50 und 200 bar das flüchtige Treibmittel eingepreßt. Dies kann diskontinuierlich in einem Druckgefäß, z.B. in einem Rührautoklaven geschehen, vorzugsweise wird aber kontinuierlich mit einem üblichen Ein- oder Zweiwellenextruder gearbeitet.#To produce the foams, the mixture of the styrene polymer and melted polyphenylene oxide. In this melt is then preferably at Temperatures between 200 and 25,000 under a pressure of 25 to 250 bar, preferably between 50 and 200 bar, the volatile propellant is injected. This can be discontinuous in a pressure vessel, e.g. in a stirred autoclave, but preferably worked continuously with a conventional single or twin screw extruder.

Kunststoff und Treibmittel werden homogen gemischt, dann wird die Mischung auf Atmosphärendruck entspannt, zweckmäßigerweise durch Auspressen aus einer Düse. Dabei verdampft das Treibmittel und der Kunststoff expandiert. Es hat sich gezeigt, daß besonders formstabile Schaumstoffe entstehen, wenn das Entspannen bei einer Temperatur vorgenommen wird, die 10 bis 40°C, vorzugsweise 20 bis 3000 über der Erweichungstemperatur (nach DIN 53 460) der thermoplastischen Kunststoffmischung liegt. Es entsteht ein Schaumstofe, dessen Querschnitt Je nach der Form der Düse rund oder rechteckig sein kann. Durch Abkühlen stabilisiert sich der Schaumstoff.Plastic and propellant are mixed homogeneously, then the Mixture relaxed to atmospheric pressure, expediently by pressing out a nozzle. The propellant evaporates and the plastic expands. It has It has been shown that particularly dimensionally stable foams are produced when the relaxation is carried out is carried out at a temperature which is 10 to 40 ° C, preferably 20 to 3000 above the softening temperature (according to DIN 53 460) of the thermoplastic plastic mixture lies. The result is a foam, the cross-section of which depends on the shape of the nozzle can be round or rectangular. The foam stabilizes when it cools down.

Die erflndungsgemäß hergestellten Schaumstoffe weisen ebensogute mechanische und Wärmeisolier-Eigenschaften auf wie solche aus Polystyrol, ihr Raumgewicht entspricht dem eines Schaumpolystyrols, das unter vergleichbaren Bedingungen hergestellt wurde, sie zeichnen sich jedoch durch eine wesentlich höhere Formbeständigkeit in der Wärme (nach DIN 18 164 bei Belastung 5 KN/m2) aus. Sie können überall dort mit Vorteil als Isoliermaterialien eingesetzt werden, wo diese Eigenschaft von Bedeutung ist.The foams produced according to the invention have just as good mechanical properties and thermal insulation properties like those made of polystyrene, according to their density that of a foam polystyrene produced under comparable conditions, however, they are characterized by a significantly higher dimensional stability under heat (according to DIN 18 164 with a load of 5 KN / m2). You can go anywhere with advantage be used as insulating materials where this property is important.

Die im Beispiel genannten Teile und Prozente beziehen sich auf das Gewicht.The parts and percentages given in the example relate to the Weight.

beispiel In einem Rührautoklaven wurden 30 Teile Kunststoff zusammen mit 0>15 Teilen Bariumstearat als Keimbildner bei 215 0c aufgeschmolzen. Bei dieser Temperatur wurden mit einem Druck von 150 bar 3 Teile n-Pentan eingepreßt und 30 Min. lang intensiv gemischt. Danach wurde die Mischung auf die jeweilige Entspannungstemperatur abgekühlt.example 30 parts of plastic were put together in a stirred autoclave melted with 0> 15 parts of barium stearate as a nucleating agent at 215 ° C. at At this temperature, 3 parts of n-pentane were injected at a pressure of 150 bar and mixed intensively for 30 minutes. Then the mixture was adjusted to the respective Relaxation temperature cooled.

Tabelle 1 zeigt die Versuchsbedingungen und die Eigenschaften der erhaltenen Schaumstoffe.Table 1 shows the test conditions and the properties of the obtained foams.

Tabelle 1 Versuch % PPO Entspannungs- Raumge- Wärmeformin der temperatur gewicht beständig-Mischung keit 1 0 120°C 70g.l-1 87°c 2 25 140°C 65g.l-1 121°C 3 45 18000 55g.l-1 14400Table 1 Test% PPO relaxation room heat form in the temperature weight resistant-mixture speed 1 0 120 ° C 70g.l-1 87 ° C 2 25 140 ° C 65g.l-1 121 ° C 3 45 18000 55g.l-1 14400

Claims (3)

Patentanstrüche 1. Verfahren zur Herstellung von Schaumstoffen durch Aufschmelzen eines thermoplastischen Kunststoffs, Vermischen mit einem flüchtigen Treibmittel bei einem Druck von 25 bis 250 bar, Entspannen der Mischung auf Atmosphärendruck und Abkühlen des Schaumstoffs, dadurch gekennzeichnet, daß der Kunststoff ein Gemisch ist aus A. 95 bis 20 Gew.- eines Styrolpolymerisats und B. 5 bis 80 Gew.-% Polyphenylenoxid. Claims 1. Process for the production of foams by Melting a thermoplastic material, mixing it with a volatile one Propellant at a pressure of 25 to 250 bar, releasing the pressure of the mixture to atmospheric pressure and cooling the foam, characterized in that the plastic is a mixture is made of A. 95 to 20 wt .-% of a styrene polymer and B. 5 to 80 wt .-% polyphenylene oxide. 2. Verfahren zur Herstellung von Schaumstoffen nach Anspruch 1, dadurch gekennzeichnet, daS es kontinuierlich in einem Extruder durchgeführt wird 2. Process for the production of foams according to claim 1, characterized characterized in that it is carried out continuously in an extruder 3. Verfahren zur Herstellung von Schaumstoffen nach Anspruch 1, dadurch gekennzeichnet, daS das Entspannen der Mischung bei einer Temperatur vorgenommen wird, die 10 bis 4000 höher ist als die Erweichungstemperatur der Kunststoffmischung.3. Procedure for the production of foams according to claim 1, characterized in that the Relaxing the mixture is made at a temperature that is 10 to 4000 higher is than the softening temperature of the plastic mixture.
DE19823220856 1981-06-04 1982-06-03 Process for the preparation of foams Withdrawn DE3220856A1 (en)

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0166820A1 (en) * 1984-05-18 1986-01-08 Firma Carl Freudenberg Method of producing foamed resins with high dimensional stability under heat
EP0241258A2 (en) * 1986-04-07 1987-10-14 The Dow Chemical Company Expandable polymeric composition and method
EP0297293A2 (en) * 1987-07-03 1989-01-04 HERMANN BERSTORFF Maschinenbau GmbH Method and extrusion installation for the manufacturing of a foamable mixture of plastics
US4904702A (en) * 1986-12-30 1990-02-27 General Electric Company Foamable engineering thermoplastic compositions
US4927859A (en) * 1988-05-25 1990-05-22 Basf Aktiengesellschaft Expandable polymers in particle form
EP0438708A2 (en) * 1990-01-10 1991-07-31 BASF Aktiengesellschaft Foam boards with high heat distortion resistance
EP0442102A1 (en) * 1990-02-12 1991-08-21 General Electric Company Polyphenylene oxide-recycled polystyrene composition and method
US5064869A (en) * 1989-12-27 1991-11-12 General Electric Company Polyphenlene ether foams from low i.v. polyphenylene ether expandable microparticles
US5091256A (en) * 1989-12-27 1992-02-25 General Electric Company Polyphenylene ether foams from low I.V. polyphenylene ether expandable microparticles
US5093375A (en) * 1989-02-14 1992-03-03 Basf Aktiengesellschaft Bead-like expandable molding materials having high heat distortion resistance and their preparation
US5095041A (en) * 1989-12-27 1992-03-10 General Electric Company Simple process for imbibing blowing agents in thermoplastic resin granules
US5145877A (en) * 1990-02-12 1992-09-08 General Electric Co. Polyphenylene oxide-recycled polystyrene composition and method
EP0623491A1 (en) * 1993-05-03 1994-11-09 Reydel Multilayered product, particularly adaptor for providing vehicle interior cover sheets

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0166820A1 (en) * 1984-05-18 1986-01-08 Firma Carl Freudenberg Method of producing foamed resins with high dimensional stability under heat
EP0241258A2 (en) * 1986-04-07 1987-10-14 The Dow Chemical Company Expandable polymeric composition and method
EP0241258A3 (en) * 1986-04-07 1988-10-26 The Dow Chemical Company Expandable polymeric composition and method
US4904702A (en) * 1986-12-30 1990-02-27 General Electric Company Foamable engineering thermoplastic compositions
EP0297293A2 (en) * 1987-07-03 1989-01-04 HERMANN BERSTORFF Maschinenbau GmbH Method and extrusion installation for the manufacturing of a foamable mixture of plastics
DE3722050A1 (en) * 1987-07-03 1989-01-19 Berstorff Gmbh Masch Hermann METHOD AND EXTRUDER SYSTEM FOR PRODUCING A FOAMABLE PLASTIC MIXTURE
EP0297293A3 (en) * 1987-07-03 1990-03-14 HERMANN BERSTORFF Maschinenbau GmbH Method and extrusion installation for the manufacturing of a foamable mixture of plastics
US4927859A (en) * 1988-05-25 1990-05-22 Basf Aktiengesellschaft Expandable polymers in particle form
US5093375A (en) * 1989-02-14 1992-03-03 Basf Aktiengesellschaft Bead-like expandable molding materials having high heat distortion resistance and their preparation
US5064869A (en) * 1989-12-27 1991-11-12 General Electric Company Polyphenlene ether foams from low i.v. polyphenylene ether expandable microparticles
US5091256A (en) * 1989-12-27 1992-02-25 General Electric Company Polyphenylene ether foams from low I.V. polyphenylene ether expandable microparticles
US5095041A (en) * 1989-12-27 1992-03-10 General Electric Company Simple process for imbibing blowing agents in thermoplastic resin granules
US5071703A (en) * 1990-01-10 1991-12-10 Basf Aktiengesellschaft Foam sheets of high heat distortion resistance
EP0438708A3 (en) * 1990-01-10 1992-01-15 Basf Aktiengesellschaft Foam boards with high heat distortion resistance
EP0438708A2 (en) * 1990-01-10 1991-07-31 BASF Aktiengesellschaft Foam boards with high heat distortion resistance
EP0442102A1 (en) * 1990-02-12 1991-08-21 General Electric Company Polyphenylene oxide-recycled polystyrene composition and method
US5145877A (en) * 1990-02-12 1992-09-08 General Electric Co. Polyphenylene oxide-recycled polystyrene composition and method
US5147894A (en) * 1990-02-12 1992-09-15 General Electric Co. Polyphenylene oxide-recycled polystyrene composition and method
EP0623491A1 (en) * 1993-05-03 1994-11-09 Reydel Multilayered product, particularly adaptor for providing vehicle interior cover sheets
FR2704804A1 (en) * 1993-05-03 1994-11-10 Reydel Dev Laminate product intended in particular to achieve interior body trim elements.

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