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WO2009037236A1 - Polystyrène ignifugé et polystyrène modifié résistant aux chocs - Google Patents

Polystyrène ignifugé et polystyrène modifié résistant aux chocs Download PDF

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Publication number
WO2009037236A1
WO2009037236A1 PCT/EP2008/062270 EP2008062270W WO2009037236A1 WO 2009037236 A1 WO2009037236 A1 WO 2009037236A1 EP 2008062270 W EP2008062270 W EP 2008062270W WO 2009037236 A1 WO2009037236 A1 WO 2009037236A1
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weight
component
molding compositions
thermoplastic molding
components
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Christian Schade
Maarten Staal
Piyada Charoensirisomboon
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BASF SE
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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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons

Definitions

  • the invention relates to thermoplastic molding compositions containing
  • PS polystyrene
  • HIPS impact-modified polystyrene
  • B2) a phosphorus-containing flame retardant compound and B3) a fluorine-containing polymer
  • weight percentages are based on the total weight of components A) to
  • the present invention relates to processes for the preparation of such molding compositions, the use of such molding compositions for the production of moldings, fibers, foams and films as well as the moldings, fibers, foams and films obtainable in this case.
  • Expandable graphite which is also referred to as expandable graphite, as a flame retardant in polystyrene (PS) or impact modified polystyrene (HIPS) use is known for example from WO 03/046071 A1.
  • a halogen-containing compound in amounts of 2 to 11%, calculated as halogen, is needed.
  • Halogen-free flame-retardant styrene polymers containing expandable graphite and a phosphorus compound as flame retardant components are disclosed in WO 00/34367 and WO 00/34342.
  • molding compositions based on such flame-retardant styrene polymers are in terms of their dripping behavior in case of fire in need of improvement.
  • WO 2005/103136 discloses flame-retardant styrene polymers which, in addition to expandable graphite and a phosphorus compound, contain a further co-additive which is intended to suppress the migration of the phosphorus-containing flame retardant to the polymer surface.
  • Polycarbonate is explicitly mentioned as a co-additive.
  • KR1996-0001006 discloses flame-retardant polystyrene wherein the flame retardant components include expandable graphite, a phosphorus compound, and Teflon.
  • the mean particle size of the expandable graphite is 5 ⁇ m.
  • the teflon added as an anti-dripping agent is used in amounts of from 1 to 5 percent by weight.
  • the halogen-free flameproofed molding compositions obtained in this way have good heat resistance and impact resistance.
  • Object of the present invention was to find a flame retardant combination for polystyrene and impact modified polystyrene, which has an improved combination of flame retardant and mechanical properties over known systems.
  • the molding compositions defined above were found, it being essential to the invention that the expandable graphite B1) has an average particle size D50 between 10 ⁇ m and 1000 ⁇ m (measured by the method described in the example section), and the weight fraction of the fluorine-containing polymer B3) the total weight of components A) to D) is from 0.01 to 0.5% by weight.
  • novel molding compositions based on polystyrene and impact-modified polystyrene exhibit. known systems an improved combination of flame retardant and mechanical properties.
  • weight percentages are based on the total weight of components A) to
  • the flame retardant component B) comprises in particular B1) from 20 to 79.99% by weight, preferably from 30 to 69.9% by weight, particularly preferably from 40 to 59.5% by weight, of component B1), B2) from 20 to 79.99% by weight %, preferably 30 to 69.9 wt .-%, particularly preferably 40 to 59.5 wt .-%, of component B2) and B3) 0.01 to 4 wt .-%, preferably 0.1 to 3 wt. -%, more preferably 0.5 to 2
  • weight percentages are based in each case on the total weight of the components B1) to B3) and together give 100% by weight.
  • the expandable graphite B1) has an average particle size D50 between 10 ⁇ m and 1000 ⁇ m, preferably between 30 ⁇ m and 850 ⁇ m, particularly preferably between 200 ⁇ m and 700 ⁇ m (measured by the method described in the example section), and Polymer B3) based on the total weight of components A) to D) of 0.01 to 0.5 wt .-%, preferably from 0.1 to 0.45 wt .-%, particularly preferably from 0.2 to 0, 4 wt .-%, is.
  • thermoplastic molding compositions As component A) of the thermoplastic molding compositions it is possible in principle to use all polystyrenes known in the art and described in the literature and impact-modified polystyrenes or mixtures thereof.
  • PS and HIPS and their preparation, structure and properties are described in detail in the literature, for example in A. Echte, F. Haaf, J. Hambrecht, Angew. Chem. (Int Ed. Engl.) 20 (1981) 344-361, or in Kunststoffhandbuch, Vol. 4, polystyrene, Carl Hanser Verlag, 1996.
  • Suitable PS is prepared by the method of anionic or radical polymerization.
  • the influenceable by the polymerization non-uniformity of the polymer is of secondary importance.
  • PS and HIPS whose toluene-soluble fraction has an average molecular weight Mw of from 50,000 to 500,000 g / mol and which are optionally also provided with additives, such as, for example, mineral oil, stabilizers, antistatic agents or waxes, are preferred.
  • the impact-resistant polystyrenes used can also be structurally modified by the use of specific polybutadiene rubbers, for example with a 1, 4-cis or 1, 4-trans proportion or 1, 2 and 1, 4 linkage fraction modified compared to conventional rubbers be. Further, instead of polybutadiene rubbers, other diene rubbers and elastomers of the ethylene-propylene-diene copolymer type (diene rubbers) and hydrogenated diene rubbers may also be used.
  • thermoplastic molding compositions contain as component B) according to the invention containing a flame retardant mixture
  • the molding compositions according to the invention contain as component B1) known to the expert and described in the literature expandable graphite, so-called
  • Expandable graphite heat or heat expandable graphite This is usually derived from natural or artificial graphite.
  • the expandable graphite is obtainable, for example, by oxidation of natural and / or artificial graphite.
  • oxidation agents can be H2O2 or nitric acid in
  • Sulfuric acid can be used.
  • the expandable graphite may be reduced by reduction, e.g. be prepared with sodium naphthalenide in an aprotic organic solvent.
  • interstitial compounds Due to its layered lattice structure, graphite is able to form special forms of intercalation compounds. In these so-called interstitial compounds are foreign atoms or molecules in z.T. Stoichiometric ratios have been included in the spaces between the carbon atoms.
  • the surface of the expanded graphite may be better for compatibility.
  • the thermoplastic matrix may be coated with a coating agent, for example with silane sizes known to those skilled in the art.
  • the expandable graphite by o.g. Oxidation it may be necessary to add an alkaline compound, since the expandable graphite (by containing acid) may otherwise cause corrosion of the molding compositions and / or storage and Herstellapparate such molding compounds.
  • alkali metal compounds and Mg (OH) 2 or Al hydroxides can be added in amounts of up to 10, preferably up to 5 wt .-% (based on 100 wt .-% B1). The mixture is advantageously carried out before the components are compounded.
  • the heat expansion of the expandable graphite with rapid heating from room temperature to 800 ° C. is preferably at least 100 ml / g, preferably at least 110 ml / g (so-called specific volume change).
  • Essential for the suitability as a flame retardant is that the expandable graphite does not expand to a greater extent at temperatures below 270 0 C, preferably below 280 0 C.
  • the coefficient of expansion usually means the difference between the specific volume (ml / g) after heating and the specific volume at 20 ° C. room temperature. This is generally measured by the following method: A quartz vessel is heated to 1000 0 C in an electric melting furnace. 2 g of expandable graphite are quickly added to the quartz container and this 10 sec. Left in the furnace.
  • the mean particle size D 5 o of the expanded graphite should preferably be in the above-mentioned ranges. If the mean particle sizes are lower, as a rule no sufficient flameproofing effect is achieved; If they are larger, usually the mechanical properties of the thermoplastic molding compositions are adversely affected.
  • the density of the expandable graphite is usually in the range of 0.4 to 2 g / cm 3 .
  • the phosphorus-containing compounds of component B2) are organic and inorganic phosphorus-containing compounds in which the phosphorus has the valence state -3 to +5.
  • the term "level of oxidation” is understood to mean the term "oxidation state” as used in the textbook of inorganic chemistry by A.F. Hollemann and E. Wiberg, Walter des Gruyter and Co. (1964, 57th to 70th edition), pages 166 to 177, is reproduced.
  • Phosphorus compounds of valence levels -3 to +5 are derived from phosphine (-3), diphosphine (-2), phosphine oxide (-1), elemental phosphorus (+0), hypophosphorous acid (+1), phosphorous acid (+3 ), Hypophosphoric acid (+4) and phosphoric acid (+5).
  • phosphorus compounds suitable as component B2 in particular the inorganic or organic phosphates, phosphites, phosphonates, phosphate esters, red phosphorus and triphenylphosphine oxide, only a few examples are mentioned.
  • phosphorus compounds of the phosphine class which have the valence state -3 are aromatic phosphines, such as triphenylphosphine, tritolylphosphine, trinonylphosphine, trinaphthylphosphine and trisnonylphenylphosphine, among others. Triphenylphosphine is particularly suitable.
  • Examples of phosphorus compounds of the diphosphine class which have the valence state -2 are tetraphenyldiphosphine, tetranaphthyldiphosphine and the like. Particularly suitable is tetranaphthyldiphosphine.
  • Phosphorus compounds of valence state -1 are derived from the phosphine oxide.
  • R 1 , R 2 and R 3 in formula I mean the same or different alkyl, aryl, alkylaryl or cycloalkyl groups having 8 to 40 carbon atoms.
  • phosphine oxides are triphenylphosphine oxide, tritolylphosphine oxide, trisynylphenylphosphine oxide, tricyclohexylphosphine oxide, tris (n-butyl) phosphine oxide, tris (n-hexyl) phosphine oxide, tris (n-octyl) phosphine oxide, tris (cyanoethyl) - phosphine oxide, benzyl bis (cyclohexyl) phosphine oxide, benzyl bisphenyl phosphine oxide, phenyl bis (n-hexyl) phosphine oxide.
  • oxidized reaction products of phosphine with aldehydes especially from t-butylphosphine with glyoxal.
  • Particular preference is given to using triphenylphosphine oxide, tricyclohexlyphosphine oxide, tris (n-octyl) phosphine oxide and tris (cyanoethyl) phosphine oxide, in particular triphenylphosphine oxide.
  • triphenylphosphine sulfide and its derivatives of phosphine oxides as described above.
  • Phosphorus of the valence state +0 is the elemental phosphorus. Eligible are red and black phosphorus. Preference is given to red phosphorus.
  • Phosphorus compounds of the "oxidation state" +1 are, for example, hypophosphites of purely organic nature, for example organic hypophosphites, such as cellulose hypophosphite esters, esters of hypophosphorous acids with diols, for example of 1,10-dodecyldiol. Also substituted phosphinic acids and their anhydrides, such as diphenylphosphinic can be used.
  • diphenylphosphinic acid di-p-tolylphosphinic acid, di-cresylphosphinic anhydride
  • compounds such as hydroquinone, ethylene glycol, propylene glycol bis (diphenylphosphinic) - esters, inter alia, in question.
  • aryl (alkyl) phosphinic acid amides such as, for example, diphenylphosphinic acid dimethylamide and sulfonamidoaryl (alkyl) phosphinic acid derivatives, for example p-tolylsulfonamidodiphenylphosphinic acid.
  • Hydroquinone and ethylene glycol bis (diphenylphosphinic) esters and the bis-diphenylphosphinate of hydroquinone are preferably used.
  • Phosphorus compounds of the oxidation state +3 are derived from the phosphorous acid. Suitable are cyclic phosphonates derived from pentaerythritol, neopentyl glycol or catechol, e.g. Compounds according to formula II
  • +3 valence phosphorous is in triaryl (alkyl) phosphites, e.g. Triphenyl phosphite, tris (4-decylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite or phenyldidecyl phosphite and the like. contain. But there are also diphosphites, such. Propylene glycol-1, 2-bis (diphosphite) or cyclic phosphites derived from pentaerythritol, neopentyl glycol or catechol, in question.
  • methyl neopentyl glycol phosphonate and phosphite and dimethyl pentaerythritol diphosphonate and phosphite are particularly preferred.
  • hypodiphosphates such as. Tetraphenyl hypodiphosphate or Bisneopentylhypodiphosphat into consideration.
  • Suitable phosphorus compounds of the oxidation state +5 are, in particular, alkyl- and aryl-substituted phosphates.
  • Examples are phenylbisdodecylphosphate, phenylethylhydrogenphosphate, phenylbis (3,5,5-trimethylhexyl) phosphate, ethyldiphenylphosphate, 2-ethylhexyldi (tolyl) phosphate, diphenylhydrogenphosphate, bis (2-ethylhexyl) -p-tolylphosphate, tritolylphosphate, bis (2-ethylhexyl) phenyl phosphate, di (nonyl) phenyl phosphate, phenylmethyl hydrogen phosphate, di (dodecyl) p-tolyl phosphate, p-tolyl bis (2,5,5-trimethylhexyl) phosphate or 2-ethylhexy
  • phosphorus compounds in which each radical is an aryloxy radical are particularly suitable.
  • R 4 -R 7 is an aromatic radical having 6 to 20 C atoms, preferably a phenyl radical which may be substituted by alkyl groups having 1 to 4 C atoms, preferably methyl,
  • R 8 is a divalent phenol radical, preferred
  • n an average value between 0.1 to 100, preferably 0.5 to 50, in particular 0.8 to 10 and very particularly 1 to 5.
  • cyclic phosphates can also be used. Particularly suitable here is diphenylpentaerythritol diphosphate and phenylneopentyl phosphate.
  • Such polymeric, halogen-free organic phosphorus compounds containing phosphorus in the polymer chain are formed, for example, in the preparation of pentacyclic, unsaturated phosphine dihalides, as described, for example, in DE-A 20 36 173.
  • the molecular weight measured by vapor pressure osmometry in di methylformamide, the Polyphospholinoxide should be in the range of 500 to 7000, preferably in the range of 700 to 2000.
  • the phosphorus here has the oxidation state -1.
  • inorganic coordination polymers of aryl (alkyl) phosphinic acids such as e.g. Poly-ß-sodium (l) -methylphenylphosphinat be used. Their preparation is given in DE-A 31 40 520. The phosphorus has the oxidation number +1.
  • halogen-free polymeric phosphorus compounds may be prepared by the reaction of a phosphonic acid chloride, such as a phosphonic acid chloride.
  • a phosphonic acid chloride such as a phosphonic acid chloride.
  • Phenyl, methyl, propyl, styryl and vinylphosphonic dichloride with bifunctional phenols, e.g. Hydroquinone, resorcinol, 2,3,5-trimethylhydroquinone, bisphenol-A, tetramethylbiphenol-A arise.
  • polymeric phosphorus compounds which may be present in the molding compositions according to the invention are prepared by reaction of phosphorus oxytrichloride or phosphoric ester dichlorides with a mixture of mono-, bi- and trifunctional phenols and compounds carrying other hydroxyl groups (see Houben-Weyl-Chem. Müller, Thieme-Verlag Stuttgart, Organic Phosphorus Compounds Part II (1963)).
  • polymeric phosphonates can be prepared by transesterification reactions of phosphonic acid esters with bifunctional phenols (cf., DE-A 29 25 208) or by reactions of phosphonic acid esters with diamines or diamides or hydrazides (cf., US Patent 4,403,075).
  • inorganic poly ammonium phosphate
  • R 1 , R 2 is hydrogen, C 1 - to C 6 -alkyl which optionally contains one hydroxyl group, preferably C 1 - to C 4 -alkyl, linear or branched, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl; phenyl; wherein preferably at least one radical R 1 or R 2 , in particular R 1 and R 2 is hydrogen;
  • R 3 is C 1 -C 4 -alkylene, linear or branched, eg methylene, ethylene, n-
  • Propylene iso-propylene, n-butylene, tert-butylene, n-pentylene, n-octylene, n-dodecylene;
  • Arylene e.g. Phenylene, naphthylene
  • Alkylarylene e.g. Methyl-phenylene, ethyl-phenylene, tert-butyl-phenylene, methyl-naphthylene, ethyl-naphthylene, tert-butyl-naphthylene
  • Arylalkylene e.g. Phenylmethylene, phenylethylene, phenylpropylene, phenylbutylene;
  • M is an alkaline earth, alkali metal, Al, Zn, Fe, boron;
  • n is an integer of 1 to 3;
  • n is an integer of 1 and 3 and
  • R 1 and R 2 are hydrogen, where M is preferably Ca, Zn or Al and calcium phosphinate is very particularly preferred as compound.
  • Such products are commercially available e.g. available as calcium phosphinate.
  • Suitable salts of the formula IV or V in which only one radical R 1 or R 2 is hydrogen are, for example, salts of phenylphosphinic acid, their Na and / or Ca salts being preferred.
  • Further preferred salts have a hydroxyl-containing alkyl radical R 1 and / or R 2 . These are obtainable, for example, by hydroxymethylation.
  • Preferred compounds are Ca, Zn and Al salts.
  • the mean particle size D 5 o (measured by the method described in the example section) of component B2) is preferably less than 10 ⁇ m, preferably less than 7 ⁇ m and in particular less than 5 ⁇ m.
  • the Dio value is preferably less than 4 ⁇ m, in particular 3 ⁇ m and very particularly preferably less than 2 ⁇ m.
  • Preferred dgo values are less than 40 ⁇ m and in particular less than 30 ⁇ m and very particularly preferably less than 20 ⁇ m.
  • R 1 to R 20 independently of one another hydrogen, a linear or branched alkyl group up to 6 C atoms
  • X is a single bond
  • C O, S, SO 2 , C (CH 2 ) 2
  • Preferred compounds B2) are those of the formula VI in which R 1 to R 20 independently of one another are hydrogen and / or a methyl radical.
  • R 1 to R 20 independently of one another are methyl
  • such compounds are preferred in which the radicals R 1 , R 5 , R 6 , R 10 , R 11 , R 15 , R 16 , R 20 in ortho Position to the oxygen of the phosphate group represent at least one methyl radical.
  • n in the above formula (VI) is preferably 0.5 to 5, in particular 0.7 to 2 and in particular ⁇ 1 as the average value.
  • n as an average value results from the preparation of the compounds listed above, so that the degree of oligomerization is usually less than 10 and small amounts (usually ⁇ 5 wt .-%) of triphenyl phosphate are included, this being different from batch to batch.
  • Such compounds B2) are commercially available as CR-741 from Daihachi.
  • the molding compositions contain a fluorine-containing polymer.
  • a fluorine-containing polymer Preference is given to fluorine-containing ethylene polymers. These are polymers of ethylene with a fluorine content of 55 to 76 wt .-%, preferably 70 to 76 parts by weight.
  • PTFE polytetrafluoroethylene
  • tetrafluoroethylene-hexafluoropropylene copolymers or tetrafluoroethylene copolymers with smaller proportions (generally up to 50% by weight) of copolymerizable ethylenically unsaturated monomers.
  • PTFE polytetrafluoroethylene
  • tetrafluoroethylene-hexafluoropropylene copolymers or tetrafluoroethylene copolymers with smaller proportions (generally up to 50% by weight) of copolymerizable ethylenically unsaturated monomers.
  • fluorine-containing ethylene polymers are homogeneously distributed in the molding compositions and preferably have an average particle size D 5 o in the range of 0.05 to 10 .mu.m, in particular from 0.1 to 5 .mu.m. These small particle sizes can be achieved particularly preferably by using aqueous dispersions of fluorine-containing ethylene polymers and their incorporation into a polymer melt.
  • component C in principle all block copolymers based on styrene and butadiene (SBC) known to the person skilled in the art and described in the literature are suitable.
  • SBC styrene and butadiene
  • SBC or S-TPE a linear or star-shaped styrene-butadiene block copolymer with external polystyrene blocks S and, between these, styrene-butadiene copolymer blocks with a random styrene / butadiene distribution (S / B) ra NDOM or (with a styrene S / B) tap Erzu (eg Styrolux ® or especially Styroflex ® of BASF Aktiengesellschaft, K-Resin ® of CPC; further components C) are marketed under the brand names Cariflex ®, Kraton ®, Tufprene ®, A- Saflex ®).
  • the total butadiene content of component C) is preferably in the range from 15 to 50% by weight, more preferably in the range from 25 to 40% by weight, the total styrene content is correspondingly preferably in the range from 50 to 85% by weight, more preferably in the range of 60 to 75 wt .-%.
  • the styrene-butadiene block (S / B) consists of 30 to 75% by weight of styrene and 25 to 70% by weight of butadiene.
  • a block (S / B) has a butadiene content of 35 to 70 wt .-% and a styrene content of 30 to 65 wt .-%.
  • the proportion of polystyrene blocks S is preferably in the range from 5 to 40% by weight, in particular in the range from 25 to 35% by weight, based on the total block copolymer.
  • the proportion of the copolymer blocks S / B is preferably in the range of 60 to 95 wt .-%, in particular in the range of 65 to 75 wt .-%.
  • linear styrene-butadiene block copolymers of the general structure S- (S / B) -S lying with one or more, between the two S blocks, a random styrene / butadiene distribution having blocks (S / B) ra NDOM ,
  • block copolymers are obtainable by anionic polymerization in a nonpolar solvent with the addition of a polar cosolvent or a potassium salt, as described, for example, in WO 95/35335 and WO 97/40079, respectively.
  • the vinyl content is understood to be the relative proportion of 1,2-linkages of the diene units, based on the sum of the 1,2-, 1,4-cis and 1,4-trans linkages.
  • the 1,2-vinyl content in the styrene-butadiene copolymer block (S / B) is preferably below 20%, in particular in the range from 10 to 18%, particularly preferably in the range from 12 to 16%.
  • the unsaturated components in particular those derived from butadiene, the S-TPE and SBC which can be used as component C) can also be completely or partially hydrogenated.
  • the proportion of 1,2-linkages of the diene unit before the hydrogenation step can also be up to 60%.
  • thermoplastic molding compositions may contain one or more additives other than components A), B) and C) as component D).
  • plastic additives for the purposes of the present invention are, for example, stabilizers and antioxidants, agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, dyes and pigments and plasticizers and fibers, for example glass fibers or carbon fibers.
  • Oxidation retarders and heat stabilizers that can be added to the thermoplastic molding composition according to the invention are, for. B. halides of metals of Group I of the Periodic Table, z. For example, sodium, potassium, lithium halides.
  • zinc fluoride and zinc chloride can be used.
  • sterically hindered phenols, hydroquinones, substituted members of this group, secondary aromatic amines, optionally in conjunction with phosphorus-containing acids or their salts, and mixtures of these compounds, preferably in concentrations up to 1 wt .-%, based on the weight of the thermoplastic molding compositions, can be used.
  • UV stabilizers are various substituted resorcinols, salicylates, benzotriazoles and benzophenones, which are generally used in amounts of up to 2 wt .-%, based on the weight of the thermoplastic molding compositions.
  • Lubricants and mold release agents which can generally be added in amounts of up to 1% by weight, based on the weight of the thermoplastic molding compositions, are stearic acid, stearyl alcohol, stearic acid alkyl esters and amides and esters of pentaerythritol with long-chain fatty acids.
  • stearic acid stearyl alcohol
  • stearic acid alkyl esters and amides and esters of pentaerythritol with long-chain fatty acids There may also be salts of calcium, zinc or aluminum of stearic acid and dialkyl ketones, eg. B. distearyl ketone used. Zinc, magnesium and calcium stearates and N, N'-ethylene-bis-stearamide are particularly suitable according to the invention.
  • thermoplastic molding compositions according to the invention can be prepared by processes known per se, in which mixing the starting components in conventional mixing devices such as screw extruders, Brabender mills or Banbury mills and then extruded. After extrusion, the extrudate can be cooled and comminuted. It is also possible to premix individual components and then to add the remaining starting materials individually and / or likewise mixed.
  • the mixing temperatures are usually 200 to 280 0 C.
  • components B) and C) can be premixed in a first step.
  • the premixed components B) and C) can either be formulated and granulated, for example, but they can also be used directly as Melt, for example, on the same extruder, in a subsequent second step with component A) and optionally D) melt blended.
  • This premix of the flame retardant mixture with the block copolymers based on styrene and butadiene (SBC) leads ggü. the simultaneous mixing of all components to improved mechanical properties of the thermoplastic molding compositions according to the invention.
  • novel molding compositions based on polystyrene and impact-modified polystyrene exhibit. known systems an improved combination of flame retardant and mechanical properties.
  • the molding compositions according to the invention are suitable for the production of fibers, films, moldings and foams of any kind. Fibers, films, moldings and foams containing the molding compositions according to the invention can be used, for example, as household articles, electronic components, medical devices, automotive components and building materials.
  • Particle size D 5 o [ ⁇ m] The average particle size and the particle size distribution of the expanded graphite B1) were determined from the integral volume distribution.
  • the mean particle sizes are in all cases the volume average of the particle sizes, as determined by means of laser light diffraction on a Malvern Mastersizer 2000 on dry powder. Laser light diffraction provides the integral distribution of the particle diameter of a sample. From this it can be seen how many percent of the particles have a diameter equal to or smaller than a certain size.
  • the average particle diameter which is also referred to as the D 5 o value of the integral volume distribution, is defined as the particle diameter at which 50% by weight of the particles have a smaller diameter than the diameter corresponding to the D 5 o value , Likewise, then 50 wt .-% of the particles have a larger diameter than the D 5 o value.
  • the notched impact strength ak was determined according to ISO 179 IeA (F) at 23 ° C.
  • Young's modulus [MPa] The stiffness as modulus of elasticity (modulus of elasticity) was determined in the tensile test at a tensile speed of 1 mm / min at 23 ° C according to ISO 527.
  • melt volume rate MVR 200/5 according to DIN EN ISO 1133 was determined as a measure of the flowability.
  • the viscosity number VN was determined at 23 0 C using a solution of 0.5% by weight solution of the polymer in dimethylformamide JE net according to DIN 53,726th
  • the first afterburning time t1 was measured on bars with a thickness of 1.6 mm after a first flame duration of 10 seconds and the second afterburning time t2 was measured immediately after a second flame duration of 10 seconds ,
  • the heat resistance was determined as Vicat softening temperature on standard small bars at a heating rate of 50 K / hour and a force of 49.05 N according to DIN 53460, method B.
  • a-l an impact-modified polystyrene (HIPS) having a polybutadiene content of 7.7% by weight, a flowability MVR of 9.4 ml / 10 min and a heat deflection temperature of 88 ° C.
  • HIPS impact-modified polystyrene
  • Flame retardant component B As component B1) was used:
  • b1-l expanded graphite Nord- Min® 503 from Nordmann, Rassmann, GmbH, containing 8 wt .-% sulfuric acid, with a mean particle size D 5 o of 465 microns, a free expansion (starting at about 300 0 C) of at least 150 ml / g and a bulk density of 0.5 g / ml at 20 ° C.
  • b3-l polytetrafluoroethylene PTFE TE-3893, Teflon® dispersion from the company CH Erbslöh.
  • the components A) to D) (respective parts by weight of s. Table 1) were in a Zweischnecke- extruder ZSK30 of Fa for determining the products listed in Table 1 mechanical properties. Werner & Pfleiderer injection molded at 220 0 C homogenized and standard moldings.
  • the components A) to D) were homogenized on a DSM Midiextruder and with an injection molding attachment at 220 ° C melt temperature and 60 ° C mold surface temperature to test specimens according to UL 94, vertical burning standard, extruded with a thickness of 1, 6 mm.
  • the examples show that the molding compositions according to the invention based on polystyrene and impact-modified polystyrene compared to. known systems have an improved combination of flame retardant and mechanical properties.

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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)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des matières à mouler thermoplastiques contenant A) 55 à 99 % en poids d'au moins un polystyrène (PS), d'un polystyrène modifié résistant aux chocs (HIPS) ou d'un mélange de PS et HIPS ; B) 1 à 45 % en poids d'un agent ignifuge contenant B1) un graphite expansible, B2) un composé ignifuge contenant du phosphore et B3) un polymère contenant du fluor ; C) 0 à 20 % en poids d'un copolymère en bloc à base de styrène et de butadiène (SBC) ; et D) 0 à 40 % en poids d'autres additifs. Les pourcentages en poids se rapportent respectivement au poids total des composants A) à D) et conjointement, donnent 100 % en poids. L'invention est caractérisée en ce que le graphite expansible B1) a une taille de particules moyenne D50 entre 10 µm et 1000 µm (mesurée selon le procédé décrit dans la description), et en ce que la proportion en poids du polymère contenant du fluor B3) par rapport au poids total des composants A) à D) est de 0,01 à 0,5 % en poids. L'invention concerne également un procédé de production de ces matières à mouler, l'utilisation de ces matières à mouler pour produire des corps moulés, des fibres, des mousses et des feuilles et les corps moulés, fibres, mousses et feuilles ainsi produits.
PCT/EP2008/062270 2007-09-18 2008-09-16 Polystyrène ignifugé et polystyrène modifié résistant aux chocs Ceased WO2009037236A1 (fr)

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EP07116636 2007-09-18

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Publication number Priority date Publication date Assignee Title
US8097669B2 (en) 2007-07-10 2012-01-17 Styrolution GmbH Flame-retardant elastic block copolymer
US8129455B2 (en) 2007-07-10 2012-03-06 Styrolution GmbH Flame retardant thermoplastic molding compositions
CN103613872A (zh) * 2013-10-28 2014-03-05 安徽精一机械设备有限公司 一种高阻燃聚苯乙烯保温泡沫材料
EP2905306A1 (fr) * 2014-02-10 2015-08-12 Continental Reifen Deutschland GmbH Procédé de fabrication d'un mélange de caoutchouc, mélange de caoutchouc et pneu de véhicule

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8097669B2 (en) 2007-07-10 2012-01-17 Styrolution GmbH Flame-retardant elastic block copolymer
US8129455B2 (en) 2007-07-10 2012-03-06 Styrolution GmbH Flame retardant thermoplastic molding compositions
CN103613872A (zh) * 2013-10-28 2014-03-05 安徽精一机械设备有限公司 一种高阻燃聚苯乙烯保温泡沫材料
EP2905306A1 (fr) * 2014-02-10 2015-08-12 Continental Reifen Deutschland GmbH Procédé de fabrication d'un mélange de caoutchouc, mélange de caoutchouc et pneu de véhicule

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