EP0000730A1 - 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 PDF

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EP0000730A1
EP0000730A1 EP78100501A EP78100501A EP0000730A1 EP 0000730 A1 EP0000730 A1 EP 0000730A1 EP 78100501 A EP78100501 A EP 78100501A EP 78100501 A EP78100501 A EP 78100501A EP 0000730 A1 EP0000730 A1 EP 0000730A1
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molding compositions
flame
bromine
bromine compound
flame retardant
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EP0000730B1 (en
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Helmut Dr. Hagen
Herbert Dr. Naarmann
Klaus Dr. Penzien
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BASF SE
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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
    • 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
    • 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 styrene polymers which contain an organic bromine compound as a flame retardant, and to their use for the production of self-extinguishing moldings.
  • halogenated Substances can be used as flame retardants for self-extinguishing thermoplastics. To achieve a sufficient effect, relatively large amounts of halogen compounds must 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.
  • DT-OS 25 45 223 describes thermoplastic molding compositions based on styrene polymers which contain derivatives of 1,3-thiadiazole as highly effective flame retardants.
  • Foamed polystyrene which is flame-retardant with such highly brominated thiazdiazole derivatives, has the disadvantage that a slightly yellow color is caused by the Self-absorption of the flame retardant can occur. It also shows that in some cases the mechanical properties of the foams are adversely affected.
  • the object of the invention was therefore to expand the range of highly effective flame retardants and to provide organic bromine compounds which, on account of their property profile, can be used as flame retardants for the various styrene polymers.
  • styrene polymers polystyrene and copolymers of styrene occur. Ew with up to 50 w% of comonomers in question.
  • Comonomers such as ⁇ -methylstyrene, acrylonitrile such as 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 .
  • Molding compositions which are suitable for producing self-extinguishing foams are of particular importance.
  • blowing agents they preferably contain 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. allphatic or cycloaliphatic hydrocarbons, such as propane, butane, pentane, hexane, heptane or cyclohexane; furthermore 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.
  • the molding compositions contain 0.05 to 5, preferably 0.1 to 3 percent by weight of flame retardant.
  • Organic bromine compounds which meet the above-mentioned conditions are suitable as flame retardants.
  • other, e.g. aromatically bound bromine atoms may be included.
  • This compound can be prepared from acetonitrile either by trimerization and subsequent bromination in glacial acetic acid or by bormation and subsequent trimerization.
  • the presence of other known anti-jamming agents and synergists should not be excluded in the molding compounds.
  • 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 superficially to the polymers.
  • anti-adhesive agents are particularly suitable for this.
  • finely divided silica which is preferably used in amounts of 0.005 to 0.1% by weight, based on the molding composition.
  • the polymer containing blowing agent is foamed and welded into molded parts.
  • the molding compositions can be in finely divided form, e.g. present as pearls, in the form of granules or as coarse powder, as is obtained when grinding bulk polymers.
  • the particles advantageously have a diameter of 0.1 to 6 mm, preferably 0.4 to 3 mm.
  • the molding compositions can be processed, for example, by injection molding, extrusion or foaming and sintering in molds to form self-extinguishing moldings or profiles. Because of their relatively low content of organic bromine compounds, the molding compositions according to the invention have softening points which differ only slightly from those of the polymers on which they are based.
  • 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.
  • Example 1 c is repeated using a copolymer of 90% styrene and 10% acrylonitrile. The extinction time was 0 seconds.
  • a mixture of 100 parts of a styrene polymer which was prepared by polymerizing 95 parts of styrene in the presence of 5 parts of polybutadiene, and one part of the Flame retardant I is extruded in an extruder with a slot die to films of 1 mm thickness.
  • 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 polystyrene, 1.5 parts of flame retardant I and 1 part of kaolin as a nucleating agent is introduced into this filler neck.
  • 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 I 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 after exposure Pre-expanded particles obtained from water vapor are welded in a mold to foam polystyrene blocks after further storage with water vapor for one day.
  • 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 with 0.3% powdered flame retardant I, and 0.025% silica with an average particle size of 12 / um as an anti-adhesive agent by simply drumming in Paddle mixer mixed for 3 minutes.
  • a foam is obtained from the granules by treatment with steam, and an extinction time of 0.5 seconds is measured.
  • An expandable polystyrene granulate with a content of 6.4% pentane is mixed with 0.3% by weight of powdered flame retardant X or XI and 0.025% by weight of silica as an anti-wetting agent by simply tumbling in a paddle mixer for 3 minutes.
  • a foam is obtained from the granules by treatment with steam.
  • hexabromocyclododecane (HBCD) was used as a known flame retardant.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Flammfeste thermoplastische Formmassen auf Basis von Styrolpolymerisaten, die 0,05 bis 5 Gewichtsprozent einer organischen Bromverbindung als Flammschutzmittel sowie gegebenenfalls ein Treibmittel enthalten. Die Bromverbindung enthält in Molekül einen heterocyclischen Ring mit der Gruppierung N=C-CBr3, sie ist bei einer Temperatur von mindestens 150°C thermisch stabil. Die bevorzugte Bromverbindung hat die Formel

Figure imga0001
Die Formmassen können zur Herstellung von selbstverlöschenden Formkörpern, z.B. Schaumstoffen, verwendet werden.Flameproof thermoplastic molding compositions based on styrene polymers which contain 0.05 to 5 percent by weight of an organic bromine compound as a flame retardant and, if appropriate, a blowing agent. The bromine compound contains a heterocyclic ring with the grouping N = C-CBr 3 in a molecule; it is thermally stable at a temperature of at least 150 ° C. The preferred bromine compound has the formula
Figure imga0001
 The molding compositions can be used to produce self-extinguishing moldings, for example foams.

Description

Die Erfindung betrifft flammfeste, thermoplastische Formmassen auf Basis von 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 styrene polymers which contain an organic bromine compound as a flame retardant, and to their use 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 bekannte 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 halogenated. Substances can be used as flame retardants for self-extinguishing thermoplastics. To achieve a sufficient effect, relatively large amounts of halogen compounds must 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-Thiadiazols enthalten. Geschäumtes Polystyrol, das mit solchen hochbromierten Thiazdiazolderivaten 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.DT-OS 25 45 223 describes thermoplastic molding compositions based on styrene polymers which contain derivatives of 1,3-thiadiazole as highly effective flame retardants. Foamed polystyrene, which is flame-retardant with such highly brominated thiazdiazole derivatives, has the disadvantage that a slightly yellow color is caused by the Self-absorption of the flame retardant can occur. It also shows that in some cases the mechanical properties of the foams are adversely affected.

Der Erfindung lag daher die Aufgabe zugrunde, das Angebot an hochwirksamen Flammschutzmitteln zu erweitern und organische Bromverbindungen zur Verfügung zu stellen, die aufgrund ihres Eigenschaftsbildes als Flammschutzmittel für die verschiedenen Styrolpolymerisate eingesetzt werden können.The object of the invention was therefore to expand the range of highly effective flame retardants and to provide organic bromine compounds which, on account of their property profile, can be used as flame retardants for the various styrene polymers.

Diese Aufgabe wird erfindungsgemäß gelöst durch Bromverbindungen, welche folgende Bedingungen erfüllen:

  • a) Die Verbindung enthält im Molekül mindestens einen heterocyclischen Ring mit mindestens einem Stickstoff als Heteroatom,
  • b) im Molekül ist mindestens einmal, vorzugsweise zwei-oder dreimal die Gruppierung N=C-CBr3 enthalten, wobei -N=C ein Bestandteil des heterocyclischen Ringes ist,
  • c) die Verbindung-ist bei einer Temperatur von 150°C, vorzugsweise bei 180°C, thermisch so stabil, daß bei einstündiger Temperaturbelastung der Gewichtsverlust weniger als 1% beträgt,
  • d) Derivate des 1,3,4-Thiadiazols sind ausgenommen,
  • e) die Zahl der Wasserstoffatome im Molekül ist vorzugsweise gleich oder kleiner als die Zahl der Bromatome, sie ist insbesondere kleiner als 6 und in speziellen Fällen gleich 0.
According to the invention, this object is achieved by bromine compounds which meet the following conditions:
  • a) The compound contains at least one heterocyclic ring in the molecule with at least one nitrogen as hetero atom,
  • b) the molecule contains at least once, preferably two or three times the grouping N = C - CB r 3 , where -N = C is a constituent of the heterocyclic ring,
  • c) the compound is thermally stable at a temperature of 150 ° C., preferably at 180 ° C., so that the weight loss is less than 1% at a temperature load of one hour,
  • d) derivatives of 1,3,4-thiadiazole are excluded,
  • e) the number of hydrogen atoms in the molecule is preferably equal to or less than the number of bromine atoms, it is in particular less than 6 and in special cases is 0.

Als Styrolpolymerisate kommen Polystyrol und Mischpolymerisate des Styrols mit bis zu 50 Gew.% an Comonomeren in Frage. Comonomere können z.B. α-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.As styrene polymers polystyrene and copolymers of styrene occur. Ew with up to 50 w% of comonomers in question. Comonomers such as α-methylstyrene, acrylonitrile such as 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 .

Besondere Bedeutung haben Formmassen, die sich zur Herstellung selbstverlöschender Schaumstoffe eignen. Sie enthalten als Treibmittel vorzugsweise flüssige oder gasförmige organische Verbindungen, die das Polymerisat nicht lösen und deren Siedepunkt unterhalb des Erweichungspunktes des Polymerisates liegt, z.B. allphatische 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 Treibmittelgemisehe sind anwendbar. Es ist vorteilhaft, 3 bis 10 Gewichtsprozent, bezogen auf die Formmassen, an Treibmittel zu verwenden.Molding compositions which are suitable for producing self-extinguishing foams are of particular importance. As blowing agents, they preferably contain 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. allphatic or cycloaliphatic hydrocarbons, such as propane, butane, pentane, hexane, heptane or cyclohexane; furthermore 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 Flammschutzmittel. Als Flammschutzmittel kommen organische Bromverbindungen in Frage, welche den oben genannten Bedingungen genügen. Die Bromatome sitzen im Molekül nicht direkt am heterocyclischen Ring, sondern liegen als seitenständige Tribrommethyl-Gruppen vor. Es kann angenommen werden, daß hierin die C-Br-Bindung durch die benachbarte C=N-Bindung im Ring aktiviert wird, so daß die Brom-Abspaltung erleichtert ist. Darüber hinaus können im Molekül noch weitere, z.B. aromatisch gebundene Bromatome enthalten sein.The molding compositions contain 0.05 to 5, preferably 0.1 to 3 percent by weight of flame retardant. Organic bromine compounds which meet the above-mentioned conditions are suitable as flame retardants. The bromine atoms are not located directly on the heterocyclic ring in the molecule, but are present as pendant tribromomethyl groups. It can be assumed that the C-Br bond is activated here by the adjacent C = N bond in the ring, so that the bromine elimination is facilitated. In addition, other, e.g. aromatically bound bromine atoms may be included.

Besonders geeignet als Bromverbindung ist 2,4,6-Tris-(tribrommethyl)-1,3,5-triazin der allgemeinen Formel I

Figure imgb0001
2,4,6-Tris- (tri bromomethyl) -1,3,5-triazine of the general formula I
Figure imgb0001

Diese Verbindung kann aus Acetonitril entweder durch Trimerisierung und anschließende Bromierung in Eisessig oder durch Bormierung und anschließende Trimerisierung hergestellt werden.This compound can be prepared from acetonitrile either by trimerization and subsequent bromination in glacial acetic acid or by bormation and subsequent trimerization.

Weitere geeignete Bromverbindungen sind u.a.:

  • 2-Phenyl-4,6-bis-(tribrommethyl)-1,3,5-triazin der allgemeinen Formel II
    Figure imgb0002
  • 2-Phenyl-4,6-bis-(tribrommethyl)-pyrimidin
    Figure imgb0003
  • 2-Dlbromphenyl-4,6-bis-(tribrommethyl)-pyrimidin
    Figure imgb0004
  • 2,3-Bis-(tribrommethyl)-cinoxalin
    Figure imgb0005
  • 2,4-Bis-(tribommethyl)-chinazolin
    Figure imgb0006
  • 3,5-Bis-(tribrommethyl)-thiadiazol-(1,2,4)
    Figure imgb0007
  • 2-Tribrommethyl-3,3-dimelthyl-bromindolenin
    Figure imgb0008
  • 3,5-Bis-(tribrommethyl)-oxadiazal-(1,2,4)
    Figure imgb0009
  • 2-Tribrommethyl-benzthiazol
    Figure imgb0010
  • 2-Tribrommethyl-benzoxazol
    Figure imgb0011
Other suitable bromine compounds include:
  • 2-phenyl-4,6-bis (tribromomethyl) -1,3,5-triazine of the general formula II
    Figure imgb0002
  • 2-phenyl-4,6-bis (tribromomethyl) pyrimidine
    Figure imgb0003
  • 2-Dlbromphenyl-4,6-bis (tribromomethyl) pyrimidine
    Figure imgb0004
  • 2,3-bis (tribromomethyl) cinoxaline
    Figure imgb0005
  • 2,4-bis (tribomethyl) quinazoline
    Figure imgb0006
  • 3,5-bis (tribromomethyl) thiadiazole- (1,2,4)
    Figure imgb0007
  • 2-tribromomethyl-3,3-dimethyl-bromoindolenine
    Figure imgb0008
  • 3,5-bis (tribromomethyl) oxadiazal- (1,2,4)
    Figure imgb0009
  • 2-tribromomethyl-benzothiazole
    Figure imgb0010
  • 2-tribromomethyl benzoxazole
    Figure imgb0011

Bei den Formmassen soll die Anwesenheit anderer, bekannter Eammschutzmittel 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 presence of other known anti-jamming agents and synergists should not be excluded in the molding compounds. 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.

Bei treibmittelhaltigen Styrolpolymerisaten werden vorzugsweise die organischen Bromverbindungen oberflächlich auf die Polymerisate 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.In the case of styrene polymers containing blowing agents, the organic bromine compounds are preferably applied superficially to the polymers. In order to prevent the coated polystyrene particles containing blowing agent from sticking or sticking during further processing, it is advantageous to apply anti-adhesive agents to the particles in addition to the bromine compounds. Particularly suitable for this is finely divided silica, which is preferably used in amounts of 0.005 to 0.1% by weight, based on the molding composition.

In nachfolgenden Arbeitsschritten wird das treibmittelhaltige Polymerisat aufgeschäumt und zu Formteilen verschweißt.In the subsequent steps, the polymer containing blowing agent is foamed and welded into molded parts.

Die Formmassen können in feinteiliger Form, z.B. als Perlen, in Form von Granulat oder als grobe Pulver vorliegen, wie es beim Mahlen von Substanzpolymerisaten erhalten wird. Die Teilchen haben vorteilhaft einen Durchmesser von 0,1 bis 6 mm, vorzugsweise von 0,4 bis 3 mm.The molding compositions can be in finely divided form, e.g. present as pearls, in the form of granules or as coarse powder, as is obtained when grinding bulk polymers. The particles advantageously have a diameter of 0.1 to 6 mm, preferably 0.4 to 3 mm.

Die Formmassen können beispielsweise durch Spritzgießen, Strangpressen oder Aufschäumen und Versintern in Formen zu selbstverlöschenden 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 injection molding, extrusion or foaming and sintering in molds to form self-extinguishing moldings or profiles. Because of their relatively low content of organic bromine compounds, the molding compositions according to the invention have softening points which differ only slightly from those of the polymers on which they are based.

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.
The self-extinguishing moldings produced from the molding compositions are tested as follows:
  • 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.

BeisDiel 1Bei D iel 1

Es werden jeweils 30 Teile Polystyrol und verschiedene Mengen organischer Bromverbindungen der oben aufgezeigten allgemeinen Formeln 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 350C 12 Stunden lang getrocknet. Die erhaltenen Schaumstoff-Folien sind- soweit sie die erfindungsgemäßen Bromverbindungen 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 of the general formulas shown above 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 sheet thus obtained is foamed in steam at 100 ° C for 12 hours and dried in vacuo at 35 0 C. The foam foils 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 Vergleichsversuchen wurden folgende Bromverbindungen verwendet:

  • A: Hexabromeyclododecan
  • B: Tetrabromthiophen
  • C: 5,5',7,7'-Tetrabromindigo
  • D: Hexabrombenzol
    Figure imgb0012
In some cases, dicumyl peroxide was used as a synergist. The following bromine compounds were used in comparative experiments:
  • A: Hexabromeyclododecane
  • B: Tetrabromothiophene
  • C: 5.5 ', 7.7' tetrabromo indigo
  • D: hexabromobenzene
    Figure imgb0012

Die Versuche a, b, q und r sind nicht erfindungsgemäß. Hier wird auch ein stärkeres Abtropfen beobachtet.Experiments a, b, q and r are not according to the invention. More draining is also observed here.

Beispiel 2Example 2

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.

Beispiel 3Example 3

Eine Mischung aus 100 Teilen eines Styrolpolymerisates das durch Polymerisieren von 95 Teilen Styrol in Gegenwart von 5 Teilen Polybutadien hergestellt wurde, und einem Teil des Flammschutzmittels I wird in einem Extruder mit Breitschlitzdüse zu Folien von 1 mm Dicke extrudiert. Die erhaltene Folie verlischt 1,0 Sekunden nach dem Entfernen der Flamme. Prüft man vergleichsweise eine Folie, die 1,5 Teile Hexabromcyclododecan und 0,5 Teile Dicumylperoxid enthält, so verlöscht die Folie nach 8 Sekunden.A mixture of 100 parts of a styrene polymer which was prepared by polymerizing 95 parts of styrene in the presence of 5 parts of polybutadiene, and one part of the Flame retardant I is extruded in an extruder with a slot die to films of 1 mm thickness. The film obtained extinguishes 1.0 seconds after the flame is removed. If you compare a film that contains 1.5 parts of hexabromocyclododecane and 0.5 part of dicumyl peroxide, the film extinguishes after 8 seconds.

Beispiel 4Example 4

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 Dichte von etwa 40 g/l. 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 polystyrene, 1.5 parts of flame retardant I and 1 part of kaolin as a nucleating agent is introduced into this filler neck. 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.

Beispiel 5Example 5

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 I 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 I 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 after exposure Pre-expanded particles obtained from water vapor are welded in a mold to foam polystyrene blocks after further storage with water vapor for one day. 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.

Beispiel 6Example 6

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/um 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 with 0.3% powdered flame retardant I, and 0.025% silica with an average particle size of 12 / um as an anti-adhesive agent by simply drumming in Paddle mixer mixed for 3 minutes. A foam is obtained from the granules by treatment with steam, and an extinction time of 0.5 seconds is measured.

Beispiel 7Example 7

Ein expandierbares Polystyrol-Granulat mit einem Gehalt von 6,4 % Pentan wird mit 0,3 Gew.% pulverförmigem Flammschutzmittel X bzw. XI sowie 0,025 Gew.% Kieselsäure als Antiverkelbungsmittel durch einfaches Auftrommeln im Schaufelmischer 3 Minuten vermischt. Aus dem Granulat wird durch Behandlung mit Wasserdampf ein Schaumstoff erhalten. Zum Vergleich wurde als bekanntes Flammschutzmittel Hexabrom- cyclododecan (HBCD) eingesetzt.An expandable polystyrene granulate with a content of 6.4% pentane is mixed with 0.3% by weight of powdered flame retardant X or XI and 0.025% by weight of silica as an anti-wetting agent by simply tumbling in a paddle mixer for 3 minutes. A foam is obtained from the granules by treatment with steam. For comparison, hexabromocyclododecane (HBCD) was used as a known flame retardant.

Folgende Verlöschzeiten werden an den Schaumstoffen gemessen:

  • I : 9 sec
  • II : 10 sec
  • HBCD : 20 sec.
The following extinguishing times are measured on the foams:
  • I: 9 sec
  • II: 10 sec
  • HBCD: 20 sec.

Claims (5)

1. Flammfeste, thermoplastische Formmassen auf Basis von Styrolpolymerisaten, die 0,05 bis 5 Gewichtsprozent einer organischen Bromverbindung als Flammschutzmittel sowie gegebenenfalls ein Treibmittel enthalten, dadurch gekennzeichnet, daß die Bromverbindung folgende Bedingungen erfüllt: a) die Verbindung enthält im Molekül mindestens einen heterocyclischen Ring mit mindestens einem Stickstoff als Heteroatom, b) im Molekül ist mindestens einmal die Gruppierung N=C- Br3 enthalten, wobei -N=C- ein Bestandteil des heterocyclischen Ringes ist, c) die Verbindung ist bei einer Temperatur von 150°C thermisch so stabil, daß bei einstündiger Temperaturbelastung der Gewichtsverlust weniger als 1 % beträgt, d) Derivate des 1,3,4-Thiadiazols sind ausgenommen. 1. Flame-resistant, thermoplastic molding compositions based on styrene polymers which contain 0.05 to 5 percent by weight of an organic bromine compound as a flame retardant and, if appropriate, a blowing agent, characterized in that the bromine compound fulfills the following conditions: a) the compound contains at least one heterocyclic ring with at least one nitrogen as hetero atom in the molecule, b) the molecule contains at least one group N = C - Br 3 , where -N = C- is part of the heterocyclic ring, c) the compound is so thermally stable at a temperature of 150 ° C that the weight loss is less than 1% at a temperature load of one hour, d) Derivatives of 1,3,4-thiadiazole are excluded. 2. Flammfeste, thermoplastische Formmasssn nach Anspruch 1, dadurch gekennzeichnet,. daß sie 3 bis 10 Gewichtsprozent eines flüssigen oder gasförmigen organischen Treibmittels enthalten.2. Flame retardant, thermoplastic molding material according to claim 1, characterized in that. that they contain 3 to 10 percent by weight of a liquid or gaseous organic blowing agent. 3. Flammfeste, thermoplastische Formmassen nach Anspruch 1, dadurch gekennzeichnet, daß die Bromverbindung 2,4,6-Tris-(tribrommethyl)-1,3,5-triazin ist.3. Flame-resistant, thermoplastic molding compositions according to claim 1, characterized in that the bromine compound is 2,4,6-tris (tribromomethyl) -1,3,5-triazine. 4. Verwendung der Formmassen nach Anspruch 1 zur Herstellung von selbstverlöschenden Formkörpern durch Spritzgießen, Strangpressen oder Aufschäumen und Versintern.4. Use of the molding compositions according to claim 1 for the production of self-extinguishing moldings by injection molding, extrusion or foaming and sintering. 5. Verwendung der Formmassen nach Anspruch 2 zur Herstellung von selbstverlöschenden Schaumstoffen.5. Use of the molding compositions according to claim 2 for the production of self-extinguishing foams.
EP78100501A 1977-08-03 1978-07-26 Fire-resistant polystyrene mouldings which include a nitrogen and bromine heterocyclic compound, and their applications Expired EP0000730B1 (en)

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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

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FR2250749A1 (en) 1973-11-14 1975-06-06 Dynamit Nobel Ag
DE2545223A1 (en) 1975-10-09 1977-04-14 Basf Ag SELF-EXTINGUISHING THERMOPLASTIC MOLDING COMPOUNDS

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US3843650A (en) * 1972-06-09 1974-10-22 Dow Chemical Co Tris-(polyhalophenoxy)-s-triazine
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US4046735A (en) * 1976-09-02 1977-09-06 Monsanto Company Stabilizers of nitrile polymers using triazine derivatives

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FR1506154A (en) 1966-01-05 1967-12-15 Huels Chemische Werke Ag Process for the preparation of 2- (alpha-perbromo-alkyl) -delta2-oxazolines
FR2250749A1 (en) 1973-11-14 1975-06-06 Dynamit Nobel Ag
DE2545223A1 (en) 1975-10-09 1977-04-14 Basf Ag SELF-EXTINGUISHING THERMOPLASTIC MOLDING COMPOUNDS

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Title
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