EP0000730B1 - Masses à mouler de polystyrène résistantes à la flamme qui contiennent un composé hétérocyclique azoté et bromé; leurs utilisations - Google Patents

Masses à mouler de polystyrène résistantes à la flamme qui contiennent un composé hétérocyclique azoté et bromé; leurs utilisations Download PDF

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Publication number
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
Authority
EP
European Patent Office
Prior art keywords
flame
bromine
fire
nitrogen
applications
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.)
Expired
Application number
EP78100501A
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German (de)
English (en)
Other versions
EP0000730A1 (fr
Inventor
Helmut Dr. Hagen
Herbert Dr. Naarmann
Klaus Dr. Penzien
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Publication date
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Publication of EP0000730A1 publication Critical patent/EP0000730A1/fr
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Classifications

    • 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 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.

Landscapes

  • 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)

Claims (4)

1. Matières à mouler thermoplastiques ignifuges à base de polymères du styrène, contenant 0,05 à 5% en poids d'un composé bromé organique hétérocyclique comme agent ignifugeant, ainsi qu'un agent d'expansion, caracterisées en que le composé bromé est la 2,4,6-tris(tribromométhyl)-1,3,5-triazine.
2. Matières à mouler thermoplastiques ignifuges suivant la revendication 1, caractérisées en ce qu'elles contiennent 3 à 10% en poids d'un agent d'expansion organique liquide du gazeux.
3. Utilisation des matières à mouler suivant la revendication 1 pour la fabrication de pièces façonnées auto-extinguibles par moulage par injection, moulage par extrusion ou par expansion et frittage.
4. Utilisation des matières à mouler suivant la revendication 2 pour la préparation de matériaux expansés auto-extinguibles.
EP78100501A 1977-08-03 1978-07-26 Masses à mouler de polystyrène résistantes à la flamme qui contiennent un composé hétérocyclique azoté et bromé; leurs utilisations Expired EP0000730B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2734926 1977-08-03
DE19772734926 DE2734926A1 (de) 1977-08-03 1977-08-03 Flammfeste, thermoplastische formmassen

Publications (2)

Publication Number Publication Date
EP0000730A1 EP0000730A1 (fr) 1979-02-21
EP0000730B1 true EP0000730B1 (fr) 1981-12-23

Family

ID=6015500

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100501A Expired EP0000730B1 (fr) 1977-08-03 1978-07-26 Masses à mouler de polystyrène résistantes à la flamme qui contiennent un composé hétérocyclique azoté et bromé; leurs utilisations

Country Status (6)

Country Link
US (1) US4158086A (fr)
EP (1) EP0000730B1 (fr)
JP (1) JPS5428354A (fr)
CA (1) CA1107899A (fr)
DE (2) DE2734926A1 (fr)
IT (1) IT1109429B (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4331780A (en) * 1980-03-20 1982-05-25 Phillips Petroleum Company Flame retardant transparent resinous copolymer
US4992482A (en) * 1989-07-10 1991-02-12 Huntsman Chemical Corporation Polyphenylene ether - alkenyl aromatic polymer blends having organobromine additives
US4927858A (en) * 1989-07-10 1990-05-22 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)

* Cited by examiner, † Cited by third party
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 (de) 1966-01-05 1970-11-05 Huels Chemische Werke Ag Verfahren zur Herstellung von 2-(alpha-Perbromalkyl)-delta?-oxazolinen
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 (fr) 1973-11-14 1975-07-03
DE2545223C3 (de) * 1975-10-09 1978-03-30 Basf Ag, 6700 Ludwigshafen Selbstverlöschende thermoplastische Formmassen
US4046735A (en) * 1976-09-02 1977-09-06 Monsanto Company Stabilizers of nitrile polymers using triazine derivatives

Also Published As

Publication number Publication date
EP0000730A1 (fr) 1979-02-21
DE2861450D1 (en) 1982-02-11
IT1109429B (it) 1985-12-16
US4158086A (en) 1979-06-12
JPS5428354A (en) 1979-03-02
DE2734926A1 (de) 1979-02-22
IT7850556A0 (it) 1978-08-01
CA1107899A (fr) 1981-08-25

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