EP0000730B1 - Fire-resistant polystyrene mouldings which include a nitrogen and bromine heterocyclic compound, and their applications - Google Patents
Fire-resistant polystyrene mouldings which include a nitrogen and bromine heterocyclic compound, and their applications Download PDFInfo
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- EP0000730B1 EP0000730B1 EP78100501A EP78100501A EP0000730B1 EP 0000730 B1 EP0000730 B1 EP 0000730B1 EP 78100501 A EP78100501 A EP 78100501A EP 78100501 A EP78100501 A EP 78100501A EP 0000730 B1 EP0000730 B1 EP 0000730B1
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- flame
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S260/00—Chemistry of carbon compounds
- Y10S260/24—Flameproof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S521/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S521/907—Nonurethane flameproofed cellular product
Definitions
- the invention relates to flame-resistant, thermoplastic molding compositions based on blowing agent-containing styrene polymers which contain an organic bromine compound as a flame retardant, and to the use thereof for the production of self-extinguishing moldings.
- halogen-containing substances can be used as flame retardants for self-extinguishing thermoplastics.
- relatively large amounts of halogen compounds have to be added.
- this adversely affects the mechanical properties of the plastics.
- organic bromine compounds is improved by adding organic peroxides.
- these have the disadvantage that they are toxic and sometimes decompose explosively.
- DT-OS 25 45 223 describes thermoplastic molding compositions based on styrene polymers which contain derivatives of 1,3,4-thiadiazole as highly effective flame retardants.
- Foamed polystyrene which is flame-retardant with such highly brominated thiadiazole derivatives, has the disadvantage that a slightly yellow color can occur due to the self-absorption of the flame retardant. It also shows that in some cases the mechanical properties of the foams are adversely affected.
- FR-PS 1 506 154 describes 2-tribromomethyl oxazolines which are said to be effective as flame retardants for plastics. However, these compounds are not very thermally stable, so that damage occurs when processing correspondingly flame-retardant molding compositions.
- the object of the invention was therefore to expand the range of flame retardants and to provide an organic bromine compound which, owing to its property profile, can be used as a highly effective flame retardant for blowing agent-containing styrene polymers.
- This object is achieved according to the invention if 0.05 to 5 percent by weight 2,4,6-tris (tribromomethyl) -1,3,5-triazine is used as the flame retardant for flame-retardant, thermoplastic molding compositions based on blowing agent-containing styrene polymers.
- Suitable styrene polymers are polystyrene and copolymers of styrene with up to 50% by weight of comonomers.
- Comonomers can e.g. a-Methylstyrene, acrylonitrile and esters of acrylic or methacrylic acid of alcohols with 1 to 8 carbon atoms.
- impact-modified styrene polymers which are prepared by polymerizing styrene, optionally together with acrylonitrile, in the presence of rubber-like butadiene, isoprene, ethylene / propylene or acrylic ester polymers, for example impact-resistant polystyrene with 2 to 10% by weight polybutadiene .
- the molding compositions according to the invention preferably contain, as blowing agents, liquid or gaseous organic compounds which do not dissolve the polymer and whose boiling point is below the softening point of the polymer, e.g. aliphatic or cycloaliphatic hydrocarbons, such as propane, butane, pentane, hexane, heptane or cyclohexane; also carbon dioxide or halogenated hydrocarbons such as methyl chloride, dichlorodifluoromethane or 1,2,2-trifluoro-1,1,2-trichloroethane. Blowing agent mixtures can also be used. It is advantageous to use 3 to 10 percent by weight, based on the molding compositions, of blowing agent.
- blowing agents liquid or gaseous organic compounds which do not dissolve the polymer and whose boiling point is below the softening point of the polymer, e.g. aliphatic or cycloaliphatic hydrocarbons, such as propane, butane, pentane,
- the molding compositions contain 0.05 to 5, preferably 0.1 to 3 percent by weight of the flame retardant according to the invention. The presence of other known flame retardants and synergists should not be excluded.
- the molding compositions may also contain other components, e.g. Fillers, color pigments, lubricants, plasticizers, antistatic agents, anti-aging agents, stabilizers or compounds that promote foam formation.
- the organic bromine compounds can, for example, be incorporated into the plastic on a roller, in an extruder or in a kneader. In many cases, they can also be added to the monomers before the polymerization. It is also possible, e.g. in the production of cast films, add the polymers together with the bromine compound to a solution of the plastic and evaporate the solvent.
- the organic bromine compounds are preferably applied to the surface of the blowing agent-containing styrene polymers.
- anti-adhesive agents to the particles in addition to the bromine compounds.
- Finely divided silica which is preferably used in amounts of 0.005 to 0.1% by weight, based on the molding composition, is particularly suitable for this.
- the polymer containing blowing agent is foamed and welded into molded parts.
- the molding compositions can be in finely divided form, for example in the form of beads, in the form of granules or in the form of a coarse powder, as obtained when grinding bulk polymers becomes.
- the particle chem advantageously have a diameter of 0.1 to 6 mm, preferably from 0.4 to 3 mm.
- the molding compositions can be processed, for example, by extrusion or foaming and sintering in molds to form self-extinguishing foam molded articles or profiles.
- the molding compositions according to the invention have softening points which differ from those on which they are based. Distinguish polymers only slightly.
- a particular advantage of the bromine compounds used according to the invention is their high effectiveness, even without synergistic additives, such as peroxides or azo derivatives. Furthermore, with comparable bromine content, shorter extinguishing times are achieved than with conventional flame retardants. Drainage is also significantly reduced.
- dicumyl peroxide was used as a synergist.
- bromine compounds were used in the tests:
- Example 1 c is repeated using a copolymer of 90% styrene and 10% acrylonitrile. The extinction time was 0 seconds.
- a nozzle for injecting liquids is attached to a twin-screw extruder in the first third of the cylinder.
- a mixture of 100 parts of 1.5 polystyrene is placed in this filler neck Parts of the flame retardant I and 1 part of kaolin introduced as a nucleating agent.
- the temperature in the melting zone is 180 ° C.
- quantities of methyl chloride are injected through the nozzle so that the mixture emerging at the nozzle head contains approximately 10%, based on the polystyrene, of methyl chloride.
- the temperature in the mixing zone is 160 ° C.
- the mixture is cooled to such an extent that the mixture emerging from the nozzle has a temperature of 110 ° C.
- the foam obtained has a density of about 40 g / l. The flame extinguishes practically immediately on a test specimen.
- 0.64 parts of polyvinylpyrrolidone as protective colloid and 0.6 part of sodium pyrophosphate are dissolved in 400 parts of water in a stirred vessel. 200 parts of styrene are added, in which 14 parts of pentane, 0.75 part of benzoyl peroxide and 1 part of the flame retardant 1 have previously been dissolved. The mixture is heated to 70 ° C. with stirring for 20 hours and held at 85 ° C. for a further 15 hours. The resulting blowing agent-containing polystyrene is separated off, washed and dried. The pre-expanded particles obtained after exposure to water vapor are welded into foam polystyrene blocks in one mold after storage for one day by further treatment with water vapor.
- the color of these blocks is pure white. They are cut from them with the help of an electrically heated wire foam sheets of 1.5 cm thickness. These are stored for several days at room temperature and cut to about 30 x 40 cm. Then one holds such plates with their edge in a luminous gas flame, removes this and measures the time until the foam extinguishes. The extinguishing time is 0 seconds and the samples practically do not ignite.
- An expandable polystyrene granulate with a content of 6.4% pentane and an average particle diameter of 1.5 mm is combined with 0.3% powdered flame retardant I and 0.025% silica with an average particle size of 12 pm as an anti-adhesive agent by simply tumbling in the paddle mixer Mixed for 3 minutes.
- a foam is obtained from the granules by treatment with steam and an extinguishing time of 0.5 seconds is measured.
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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Description
Die Erfindung betrifft flammfeste, thermoplastische Formmassen auf Basis von treibmittelhaltigen Styrolpolymerisaten, die eine organische Bromverbindung als Flammschutzmittel enthalten, sowie deren Verwendung zur Herstellung von selbstverlöschenden Formkörpern.The invention relates to flame-resistant, thermoplastic molding compositions based on blowing agent-containing styrene polymers which contain an organic bromine compound as a flame retardant, and to the use thereof for the production of self-extinguishing moldings.
Es ist bekannt, daß halogenhaltige Stoffe als Flammschutzmittel für selbstverlöschende thermoplastische Kunststoffe verwendet werden können. Um eine ausreichende Wirkung zu erzielen, müssen verhältnismäßig große Mengen an Halogenverbindungen zugesetzt werden. Dadurch werden jedoch die mechanischen Eigenschaften der Kunststoffe nachteilig beeinflußt. Es ist außerdem bekannt, daß die flammhemmende Wirkung organischer Bromverbindungen durch Zusatz organischer Peroxide verbessert wird. Diese haben jedoch den Nachteil, daß sie toxisch sind und sich mitunter explosionsartig zersetzen.It is known that halogen-containing substances can be used as flame retardants for self-extinguishing thermoplastics. In order to achieve a sufficient effect, relatively large amounts of halogen compounds have to be added. However, this adversely affects the mechanical properties of the plastics. It is also known that the flame retardant effect of organic bromine compounds is improved by adding organic peroxides. However, these have the disadvantage that they are toxic and sometimes decompose explosively.
In der DT-OS 25 45 223 sind thermoplastische Formmassen auf Basis von Styrolpolymerisaten beschrieben, welche als hochwirksame Flammschutzmittel Derivate des 1,3,4-Thiadiazols enthalten. Geschäumtes Polystyrol, das mit solchen hochbromierten Thiadiazolderivaten flammfest ausgerüstet ist, hat den Nachteil, daß ein leicht gelber Farbton, bedingt durch die Eigenabsorption des Flammschutzmittels, auftreten kann. Außerdem zeigt sich, daß in manchen Fällen die mechanischen Eigenschaften der Schaumstoffe ungünstig beeinflußt werden. In der FR-PS 1 506 154 sind 2-Tribrommethyl-oxazoline beschrieben, die als Flammschutzmittel für Kunststoffe wirksam sein sollen. Diese Verbindungen sind aber thermisch wenig stabil, so daß bei der Verarbeitung entsprechend flammfest ausgerüsteter Formmassen eine Schädigung eintritt.DT-OS 25 45 223 describes thermoplastic molding compositions based on styrene polymers which contain derivatives of 1,3,4-thiadiazole as highly effective flame retardants. Foamed polystyrene, which is flame-retardant with such highly brominated thiadiazole derivatives, has the disadvantage that a slightly yellow color can occur due to the self-absorption of the flame retardant. It also shows that in some cases the mechanical properties of the foams are adversely affected. FR-PS 1 506 154 describes 2-tribromomethyl oxazolines which are said to be effective as flame retardants for plastics. However, these compounds are not very thermally stable, so that damage occurs when processing correspondingly flame-retardant molding compositions.
In der FR-PS 2 250 749 und in Chemical Abstracts Vol. 78, Seite 12, Referat No. 73 139 sind halogenphenyl-substituierte Triazine beschrieben, die als Flammschutzmittel für Polystyrol geeignet sein sollen. Es hat sich gezeigt, daß solche Verbindungen bei geschäumten Styrolpolymerisaten keine ausreichende Flammschutzwirkung haben.In FR-PS 2 250 749 and in Chemical Abstracts Vol. 78, page 12, no. 73 139 describes halogen-phenyl-substituted triazines which are said to be suitable as flame retardants for polystyrene. It has been shown that such compounds do not have adequate flame retardancy in the case of foamed styrene polymers.
Der Erfindung lag daher die Aufgabe zugrunde, das Angebot an Flammschutzmitteln zu erweitern und eine organische Bromverbindung zur Verfügung zu stellen, die aufgrund ihres Eigenschaftsbildes als hochwirksames Flammschutzmittel für treibmittelhaltige Styrolpolymerisate eingesetzt werden kann. Diese Aufgabe wird erfindungsgemäß gelöst, wenn man als Flammschutzmittel für flammfeste, thermoplastische Formmassen auf Basis von treibmittelhaltigen Styrolpolymerisaten 0,05 bis 5 Gewichtsprozent 2,4,6-Tris-(tribrommethyi)-1,3,5-triazin verwendet.The object of the invention was therefore to expand the range of flame retardants and to provide an organic bromine compound which, owing to its property profile, can be used as a highly effective flame retardant for blowing agent-containing styrene polymers. This object is achieved according to the invention if 0.05 to 5 percent by weight 2,4,6-tris (tribromomethyl) -1,3,5-triazine is used as the flame retardant for flame-retardant, thermoplastic molding compositions based on blowing agent-containing styrene polymers.
Als Styrolpolymerisate kommen Polystyrol und Mischpolymerisate des Styrols mit bis zu 50 Gew.% an Comonomeren in Frage. Comonomere können z.B. a-Methylstyrol, Acrylnitril sowie Ester der Acryl- oder Methacrylsäure von Alkoholen mit 1 bis 8 Kohlenstoffatomen sein. In Betracht kommen auch schlagzäh modifizierte Styrolpolymerisate, die durch Polymerisation von Styrol, gegebenenfalls zusammen mit Acrylnitril, in Gegenwart kautschukartiger Butadien-, Isopren-, Äthylen/Propylen- oder Acrylester-Polymerisate hergestellt werden, beispielsweise schlagfestes Polystyrol mit 2 bis 10 Gew.% Polybutadien.Suitable styrene polymers are polystyrene and copolymers of styrene with up to 50% by weight of comonomers. Comonomers can e.g. a-Methylstyrene, acrylonitrile and esters of acrylic or methacrylic acid of alcohols with 1 to 8 carbon atoms. Also suitable are impact-modified styrene polymers which are prepared by polymerizing styrene, optionally together with acrylonitrile, in the presence of rubber-like butadiene, isoprene, ethylene / propylene or acrylic ester polymers, for example impact-resistant polystyrene with 2 to 10% by weight polybutadiene .
Die erfindungsgemäßen Formmassen enthalten als Treibmittel vorzugsweise flüssige oder gasförmige organische Verbindungen, die das Polymerisat nicht lösen und deren Siedepunkt unterhalb des Erweichungspunktes des Polymerisates leigt, z.B. aliphatische oder cycloaliphatische Kohlenwasserstoffe, wie Propan, Butan, Pentan, Hexan, Heptan oder Cyclohexan; ferner Kohlendioxid oder Halogenkohlenwasserstoffe wie Methylchlorid, Dichlordifluormethan oder 1,2,2-Trifluor-1,1,2-trichloräthan. Auch Treibmittelgemische sind anwendbar. Es ist vorteilhaft, 3 bis 10 Gewichtsprozent bezogen auf die Formmassen, an Treibmittel zu verwenden.The molding compositions according to the invention preferably contain, as blowing agents, liquid or gaseous organic compounds which do not dissolve the polymer and whose boiling point is below the softening point of the polymer, e.g. aliphatic or cycloaliphatic hydrocarbons, such as propane, butane, pentane, hexane, heptane or cyclohexane; also carbon dioxide or halogenated hydrocarbons such as methyl chloride, dichlorodifluoromethane or 1,2,2-trifluoro-1,1,2-trichloroethane. Blowing agent mixtures can also be used. It is advantageous to use 3 to 10 percent by weight, based on the molding compositions, of blowing agent.
Die Formmassen enthalten 0,05 bis 5, vorzugsweise 0,1 bis 3 Gewichtsprozent des erfindungsgemäßen Flammschutzmittels. Dabei soll die Anwesenheit anderer, bekannter Flammschutzmittel und Synergisten nicht ausgeschlossen sein. Die Formmassen können noch weitere Komponenten enthalten, z.B. Füllstoffe, Farbpigmente, Gleitmittel, Weichmacher, Antistatika, Alterungsschutzmittel, Stabilisatoren oder solche Verbindungen, welche die Schaumbildung fördern.The molding compositions contain 0.05 to 5, preferably 0.1 to 3 percent by weight of the flame retardant according to the invention. The presence of other known flame retardants and synergists should not be excluded. The molding compositions may also contain other components, e.g. Fillers, color pigments, lubricants, plasticizers, antistatic agents, anti-aging agents, stabilizers or compounds that promote foam formation.
Die organischen Bromverbindungen können beispielsweise auf der Walze, im Extruder oder in einem Kneter in den Kunststoff eingearbeitet werden. In vielen Fällen können sie auch bereits vor der Polymerisation den Monomeren zugesetzt werden. Es ist auch möglich, z.B. bei der Herstellung von Gießfolien, die Polymeren zusammen mit der Bromverbindung einer Lösung des Kunststoffes zuzusetzen und das Lösungsmittel abzudampfen.The organic bromine compounds can, for example, be incorporated into the plastic on a roller, in an extruder or in a kneader. In many cases, they can also be added to the monomers before the polymerization. It is also possible, e.g. in the production of cast films, add the polymers together with the bromine compound to a solution of the plastic and evaporate the solvent.
Vorzugsweise werden die organischen Bromverbindungen oberflächlich auf die treibmittelhaltigen Styrolpolymerisate aufgebracht. Um ein Verbacken oder Verkleben der beschichteten treibmittelhaltigen Polystyrol-Teilchen bei der Weiterverarbeitung zu verhindern, ist es vorteilhaft, zusätzlich zu den Bromverbindungen noch Antiverklebungsmittel auf die Teilchen aufzubringen. Besonders geeignet dafür ist feinteilige Kieselsäure, die vorzugsweise in Mengen von 0,005 bis 0,1 Gew.% bezogen auf die Formmasse, eingesetzt wird.The organic bromine compounds are preferably applied to the surface of the blowing agent-containing styrene polymers. In order to prevent caking or sticking of the coated blowing agent-containing polystyrene particles during further processing, it is advantageous to apply anti-adhesive agents to the particles in addition to the bromine compounds. Finely divided silica, which is preferably used in amounts of 0.005 to 0.1% by weight, based on the molding composition, is particularly suitable for this.
In nachfolgenden Arbeitsschritten wird das treibmittelhaltige Polymerisat aufgeschäumt und zu Formteilen verschweißt. Die Formmassen können in feinteiliger Form, z.B. als Perlen, in Form von Granulat oder als grobes Pulver vorliegen, wie es beim Mahlen von Substanzpolymerisaten erhalten wird. Die Teilchem haben vorteilhaft einen Durchmesser von 0,1 bis 6 mm, vorzugsweise von 0,4 bis 3 mm.In the subsequent steps, the polymer containing blowing agent is foamed and welded into molded parts. The molding compositions can be in finely divided form, for example in the form of beads, in the form of granules or in the form of a coarse powder, as obtained when grinding bulk polymers becomes. The particle chem advantageously have a diameter of 0.1 to 6 mm, preferably from 0.4 to 3 mm.
Die Formmassen können beispielsweise durch Strangpressen oder Aufschäumen und Versintern in Formen zu selbstverlöschenden Schaumstoff-Formkörpern oder -Profilen verarbeitet werden. Aufgrund ihres relativ geringen Gehaltes an organischen Bromverbindungen haben die erfindungsgemäßen Formmassen Erweichungspunkte, die sich von denen der ihnen zugrundeliegenden. Polymerisate nur geringfügig unterscheiden.The molding compositions can be processed, for example, by extrusion or foaming and sintering in molds to form self-extinguishing foam molded articles or profiles. On account of their relatively low content of organic bromine compounds, the molding compositions according to the invention have softening points which differ from those on which they are based. Distinguish polymers only slightly.
Ein besonderer Vorteil der erfindungsgemäß eingesetzten Bromverbindungen ist ihre hohe Wirksamkeit, auch ohne synergistische Zusätze, wie Peroxide oder Azoderivate. Ferner werden bei vergleichbarem Bromanteil kürzere Verlöschzeiten als mit herkömmlichen Flammschutzmitteln erzielt. Außerdem ist das Abtropfen deutlich verringert.A particular advantage of the bromine compounds used according to the invention is their high effectiveness, even without synergistic additives, such as peroxides or azo derivatives. Furthermore, with comparable bromine content, shorter extinguishing times are achieved than with conventional flame retardants. Drainage is also significantly reduced.
Die aus den Formmassen hergestellten selbstverlöschenden Formkörper werden auf folge Weise geprüft:
- Zur Prüfung ungeschäumter Massen werden Formkörper mit der Abmessung 0,1 x 10 x 30 cm, zur Prüfung geschäumter Massen solche mit der Abmessung 0,5 x 15 x 40 cm 5 Sekunden lang in eine Gasflamme von 40 mm Flammenhöhe gehalten und die Flamme anschließend mit ruhiger Bewegung entfernt. Die Verlöschzeit des Formkörpers nach Entfernen aus der Flamme ist ein Maß für dessen Flammwidrigkeit. Die angegebenen Verlöschzeiten sind Mittelwerte aus 10 Brennproben. Ungenügend oder gar nicht schwer entflammbar ausgerüstete Formmassen brennen nach Entfernen aus der Flamme vollständig ab.
- For testing non-foamed masses, molded articles with the dimensions 0.1 x 10 x 30 cm are held for a test of foamed masses with the dimensions 0.5 x 15 x 40 cm for 5 seconds in a gas flame of 40 mm flame height and then the flame with calm movement away. The extinguishing time of the shaped body after removal from the flame is a measure of its flame resistance. The specified extinguishing times are mean values from 10 firing samples. Molding compositions that are insufficiently or not flame retardant burn completely after removal from the flame.
Die in den Beispielen genannten Teile und Prozente beziehen sich auf das Gewicht.The parts and percentages given in the examples relate to the weight.
Es werden jeweils 30 Teile Polystyrol und verschiedene Mengen organischer Bromverbindungen in 100 Teilen Methylenchlorid gelöst. Der Lösung werden 3 Teile Pentan zugesetzt. Danach gießt man die Lösung auf eine Glasplatte aus, läßt das Methylenchlorid bei Raumtemperatur verdunsten. Dabei bleibt das Pentan in homogener Verteilung in der Mischung. Die so erhaltene Folie wird in Wasserdampf von 100°C aufgeschäumt und im Vakuum bei 35°C 12 Stunden lang getrocknet. Die erhaltenen Schaumstoff-Folien sind - soweit sie die erfindungsgemäße Bromverbindunge enthalten - reinweiß. Sie werden nach der oben angegebenen Methode auf ihre Schwerentflammbarkeit geprüft. Die Ergebnisse sind in der Tabelle wiedergegeben.30 parts of polystyrene and various amounts of organic bromine compounds are dissolved in 100 parts of methylene chloride. 3 parts of pentane are added to the solution. Then the solution is poured onto a glass plate and the methylene chloride is allowed to evaporate at room temperature. The pentane remains in the mixture in a homogeneous distribution. The film obtained in this way is foamed in water vapor at 100 ° C. and dried in vacuo at 35 ° C. for 12 hours. The foam sheets obtained are - if they contain the bromine compounds according to the invention - pure white. They are tested for their flame retardancy using the method specified above. The results are shown in the table.
Als Synergist wurde in einigen Fällen Dicumylperoxid eingesetzt. In den Versuchen wurden folgende Bromverbindungen verwendet:In some cases, dicumyl peroxide was used as a synergist. The following bromine compounds were used in the tests:
Beispiel 1 c wird wiederholt, wobei ein Copolymerisat aus 90% Styrol und 10% Acrylnitril verwendet wird. Die Verlöschzeit betrug 0 Sekunden.Example 1 c is repeated using a copolymer of 90% styrene and 10% acrylonitrile. The extinction time was 0 seconds.
An einem Doppelschneckenextruder ist im ersten Drittel des Zylinders ein Stutzen zum Einpressen von Flüssigkeiten angebracht. In diesen Einfüllstutzen wird ein Gemisch aus 100 Teilen Polystyrol, 1,5 Teilen des Flammschutzmittels I und 1 Teile Kaolin als Keimbildner eingebracht. Die Temperatur beträgt in der Aufschmelzzone 180°C. In der anschließenden Mischzone werden durch den Stutzen solche Mengen Methylchlorid eingepreßt, daß die am Düsenkopf austretende Mischung etwa 10%, bezogen auf das Polystyrol, an Methylchlorid enthält. In der Mischzone beträgt die Temperatur 160°C. In der anschließenden Kühlzone wird die Mischung so weit abgekühlt, daß die aus der Düse austretende Mischung eine Temperatur von 110°C hat. Der aus der Düse austretende Strang schäumt auf. Der erhaltene Schaumstoff hat eine Dicht von etwa 40 g/I. An einem Prüfkörper verlöscht die Flamme praktisch sofort.A nozzle for injecting liquids is attached to a twin-screw extruder in the first third of the cylinder. A mixture of 100 parts of 1.5 polystyrene is placed in this filler neck Parts of the flame retardant I and 1 part of kaolin introduced as a nucleating agent. The temperature in the melting zone is 180 ° C. In the subsequent mixing zone, quantities of methyl chloride are injected through the nozzle so that the mixture emerging at the nozzle head contains approximately 10%, based on the polystyrene, of methyl chloride. The temperature in the mixing zone is 160 ° C. In the subsequent cooling zone, the mixture is cooled to such an extent that the mixture emerging from the nozzle has a temperature of 110 ° C. The strand emerging from the nozzle foams. The foam obtained has a density of about 40 g / l. The flame extinguishes practically immediately on a test specimen.
In einem Rührgefäß löst man in 400 Teilen Wasser 0,64 Teile Polyvinylpyrrolidon als Schutzkolloid und 0,6 Teile Natriumpyrophosphat. Dazu gibt man 200 Teilen Styrol, in welchem zuvor 14 Teile Pentan, 0,75 Teile Benzoylperoxid und 1 Teil des Flammschutzmittels 1 gelöst wurden. Man heizt unter Rühren während 20 Stunden auf 70°C und hält weitere 15 Stunden bei 85°C. Das entstandene treibmittelhaltige Polystyrol wird abgetrennt, gewaschen und getrocknet. Die nach Einwirkung von Wasserdampf erhaltenen vorgeschäumten Teilchen werden nach eintägiger Lagerung durch weitere Behandlung mit Wasserdampf in einer Form zu Schaumpolystyrol-Blöcken verschweißt. Die Farbe dieser Blöcke ist reinweiß. Man schneidet aus ihnen mit Hilfe eines elektrisch beheizten Drahtes Schaumstoffplatten von 1,5 cm Dicke. Diese werden mehrere Tage bei Raumtemperatur gelagert und auf etwa 30 x 40 cm zurechtgeschnitten. Anschließend hält man derartige Platten mit ihrer Kante in eine leuchtende Gasflamme, entfernt diese und mißt die Zeit bis zum Verlöschen des Schaumes. Die Verlöschzeit beträgt 0 Sekunden bzw. die Proben entflammen praktisch nicht.0.64 parts of polyvinylpyrrolidone as protective colloid and 0.6 part of sodium pyrophosphate are dissolved in 400 parts of water in a stirred vessel. 200 parts of styrene are added, in which 14 parts of pentane, 0.75 part of benzoyl peroxide and 1 part of the flame retardant 1 have previously been dissolved. The mixture is heated to 70 ° C. with stirring for 20 hours and held at 85 ° C. for a further 15 hours. The resulting blowing agent-containing polystyrene is separated off, washed and dried. The pre-expanded particles obtained after exposure to water vapor are welded into foam polystyrene blocks in one mold after storage for one day by further treatment with water vapor. The color of these blocks is pure white. They are cut from them with the help of an electrically heated wire foam sheets of 1.5 cm thickness. These are stored for several days at room temperature and cut to about 30 x 40 cm. Then one holds such plates with their edge in a luminous gas flame, removes this and measures the time until the foam extinguishes. The extinguishing time is 0 seconds and the samples practically do not ignite.
Ein expandierbares Polystyrol-Granulat mit einem Gehalt von 6,4% Pentan und einem mittleren Teilchendurchmesser von 1,5 mm wird mit 0,3% pulverförmigem Flammschutzmittel I, sowie 0,025% Kieselsäure einer mittleren Teilchengröße von 12 pm als Antiverklebungsmittel durch einfaches Auftrommeln im Schaufelmischer 3 Minuten vermischt. Aus dem Granulat wird durch Behandlung mit Wasserdampf ein Schaumstoff erhalten, an dem eine Verlöschzeit von 0,5 Sekunden gemessen wird.An expandable polystyrene granulate with a content of 6.4% pentane and an average particle diameter of 1.5 mm is combined with 0.3% powdered flame retardant I and 0.025% silica with an average particle size of 12 pm as an anti-adhesive agent by simply tumbling in the paddle mixer Mixed for 3 minutes. A foam is obtained from the granules by treatment with steam and an extinguishing time of 0.5 seconds is measured.
Claims (4)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2734926 | 1977-08-03 | ||
| DE19772734926 DE2734926A1 (en) | 1977-08-03 | 1977-08-03 | FLAME RESISTANT, THERMOPLASTIC MOLDING COMPOUNDS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0000730A1 EP0000730A1 (en) | 1979-02-21 |
| EP0000730B1 true EP0000730B1 (en) | 1981-12-23 |
Family
ID=6015500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP78100501A Expired EP0000730B1 (en) | 1977-08-03 | 1978-07-26 | Fire-resistant polystyrene mouldings which include a nitrogen and bromine heterocyclic compound, and their applications |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4158086A (en) |
| EP (1) | EP0000730B1 (en) |
| JP (1) | JPS5428354A (en) |
| CA (1) | CA1107899A (en) |
| DE (2) | DE2734926A1 (en) |
| IT (1) | IT1109429B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4331780A (en) * | 1980-03-20 | 1982-05-25 | Phillips Petroleum Company | Flame retardant transparent resinous copolymer |
| US4927858A (en) * | 1989-07-10 | 1990-05-22 | Huntsman Chemical Corporation | Polyphenylene ether-alkenyl aromatic polymer blends having organobromine additives |
| US4992482A (en) * | 1989-07-10 | 1991-02-12 | Huntsman Chemical Corporation | Polyphenylene ether - alkenyl aromatic polymer blends having organobromine additives |
| US6738661B1 (en) * | 1999-10-22 | 2004-05-18 | Biosynergetics, Inc. | Apparatus and methods for the controllable modification of compound concentration in a tube |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB950292A (en) * | 1959-12-24 | 1964-02-26 | Dow Chemical Co | Cellular foamed articles from thermoplastic alkenyl aromatic polymers |
| DE1670323A1 (en) | 1966-01-05 | 1970-11-05 | Huels Chemische Werke Ag | Process for the preparation of 2- (alpha-perbromoalkyl) -delta? -Oxazolines |
| US3843650A (en) * | 1972-06-09 | 1974-10-22 | Dow Chemical Co | Tris-(polyhalophenoxy)-s-triazine |
| US3950306A (en) * | 1972-06-09 | 1976-04-13 | The Dow Chemical Company | Tris-(polyhalophenoxy)-s-triazine flame retardants |
| JPS5082082A (en) * | 1973-11-14 | 1975-07-03 | ||
| DE2545223C3 (en) | 1975-10-09 | 1978-03-30 | Basf Ag, 6700 Ludwigshafen | Self-extinguishing thermoplastic molding compounds |
| US4046735A (en) * | 1976-09-02 | 1977-09-06 | Monsanto Company | Stabilizers of nitrile polymers using triazine derivatives |
-
1977
- 1977-08-03 DE DE19772734926 patent/DE2734926A1/en not_active Withdrawn
-
1978
- 1978-07-26 DE DE7878100501T patent/DE2861450D1/en not_active Expired
- 1978-07-26 EP EP78100501A patent/EP0000730B1/en not_active Expired
- 1978-07-28 US US05/928,814 patent/US4158086A/en not_active Expired - Lifetime
- 1978-08-01 IT IT50556/78A patent/IT1109429B/en active
- 1978-08-02 CA CA308,634A patent/CA1107899A/en not_active Expired
- 1978-08-02 JP JP9372778A patent/JPS5428354A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| IT7850556A0 (en) | 1978-08-01 |
| DE2861450D1 (en) | 1982-02-11 |
| CA1107899A (en) | 1981-08-25 |
| IT1109429B (en) | 1985-12-16 |
| DE2734926A1 (en) | 1979-02-22 |
| US4158086A (en) | 1979-06-12 |
| JPS5428354A (en) | 1979-03-02 |
| EP0000730A1 (en) | 1979-02-21 |
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