EP1409587A1 - Flammwidrige polyesterformmassen mit polyolefinadditiven - Google Patents

Flammwidrige polyesterformmassen mit polyolefinadditiven

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Publication number
EP1409587A1
EP1409587A1 EP02745385A EP02745385A EP1409587A1 EP 1409587 A1 EP1409587 A1 EP 1409587A1 EP 02745385 A EP02745385 A EP 02745385A EP 02745385 A EP02745385 A EP 02745385A EP 1409587 A1 EP1409587 A1 EP 1409587A1
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EP
European Patent Office
Prior art keywords
compositions according
molding compositions
weight
acid
total composition
Prior art date
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EP02745385A
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German (de)
English (en)
French (fr)
Inventor
Matthias Bienmüller
Michael Wagner
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Lanxess Deutschland GmbH
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Bayer AG
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Publication of EP1409587A1 publication Critical patent/EP1409587A1/de
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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
    • C08K5/17—Amines; Quaternary ammonium 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates to flame-retardant, preferably halogen-free thermoplastic molding compositions containing one or more polyesters, a flame retardant combination consisting of a phosphorus-containing compound, a nitrogenous compound, and a polyolefin compound which is used alone or together with zinc sulfide.
  • the present invention relates to the use of these molding compositions for the production of moldings, films or fibers and the moldings, films and fibers themselves.
  • Flame-proof polyester molding compounds are of great importance in the electrical / electronics sector and are used there, among other things, for the production of carriers for live parts. In addition to good flame resistance, the components must also have good mechanical and electrical properties. In particular, the provision of halogen-free molding compounds is required. There have been some developments in this field in the past.
  • JP-A 3-281 652 discloses polyalkylene terephthalate resins which, as flame retardant, have a melamine-cyanuric acid adduct and a phosphate or phosphonate, and additionally
  • JP-A 6-157 880 discloses reinforced polyalkylene terephthalates which contain melamine cyanurate as a flame retardant and a phosphorus compound.
  • JP-A 9-157 503 discloses flame retardant polyester compositions containing melamine cyanurate, phosphoric acid esters and special mold release agents. Flame-retardant reinforced polyester components are known from EP-A 903 370, which contain a combination of melamine pyrophosphate and a phosphate oligomer.
  • WO 00/11085 discloses polyester molding compositions which contain melamine cyanurate, a phosphate, filler and special mold release agents.
  • WO 00/11 071 discloses polyester compositions which contain nitrogen compounds, phosphorus compounds, metal salts and stabilizer. Nevertheless, there is still a strong need for halogen-free flame-retardant polyester molding compositions which, in addition to good flame resistance, also have improved mechanical properties such as, in particular, impact resistance and edge fiber expansion.
  • polyester molding compositions containing, as flame retardants, a combination of a phosphorus-containing compound and a nitrogenous compound, and also a polyolefin compound and optionally zinc sulfide have the desired profile of properties. It was found that the additional use of zinc sulfide leads to a further improvement in the mechanical properties of the molding compositions.
  • the invention thus relates to molding compositions containing
  • R 1 , R 2 , R 3 and R 4 independently of one another in each case optionally halogenated Ci to Cg alkyl, in each case optionally C 5 substituted by alkyl, preferably C 1 -C 4 alkyl, and / or halogen, preferably chlorine, bromine - to Cg-cycloalkyl, Cg- to C 2 -oryl or C 7 - to C ⁇ -aralkyl, or preferably phenyl,
  • n independently of one another, 0 or 1; preferably 1
  • N 0 to 50 preferably an average
  • X preferably a mono- or polynuclear aromatic radical having 6 to 30 carbon atoms, derived from diphenols.
  • Resorcinol or hydroquinone and their chlorinated or brominated derivatives.
  • Polyesters according to component A) are, on the one hand, polyalkylene terephthalates, i.e. Reaction products from preferably aromatic dicarboxylic acids or their reactive derivatives (e.g. dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or araliphatic diols and mixtures of these reaction products, on the other hand also fully aromatic polyesters, which will be described in more detail later.
  • aromatic dicarboxylic acids or their reactive derivatives e.g. dimethyl esters or anhydrides
  • aliphatic, cycloaliphatic or araliphatic diols and mixtures of these reaction products on the other hand also fully aromatic polyesters, which will be described in more detail later.
  • Polyalkylene terephthalates can be prepared from terephthalic acid (or its reactive derivatives) and aliphatic or cycloaliphatic diols with 2 to 10
  • Preferred polyalkylene terephthalates contain at least 80, preferably 90 mol%, based on the dicarboxylic acid, terephthalic acid residues and at least 80, preferably at least 90 mol%, based on the diol component, 1,3-ethylene glycol and / or 1,3-propanediol and / or butane-l, 4-residues.
  • the preferred polyalkylene terephthalates can contain up to 20 mol% of residues of other aromatic dicarboxylic acids with 8 to 14 C atoms or aliphatic dicarboxylic acids with 4 to 12 C atoms, such as residues of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid.
  • the preferred polyalkylene terephthalates can contain up to 20 mol% of other aliphatic ones Contain diols with 3 to 12 carbon atoms or cycloaliphatic diols with 6 to 21 carbon atoms, for example residues of 1,3-propanediol, 2-propanediol-1,3, neopentylglycol, 1,5-pentanediol, 1-hexanediol , 6, cyclohexane-dimethanol-1,4, 3-methylpentanediol-2,4, 2-methylpentanediol-2,4, 2,2,4-trimethylpentanediol-1,3, and 1,6,2-ethyl-hexanediol -1,3 2,2-diethylpropanediol-1,3, hexaned
  • the polyalkylene terephthalates can be prepared by incorporating relatively small amounts of trihydric or tetravalent alcohols or trihydric or tetravalent carboxylic acids, e.g. are described in DE-OS 19 00 270 and US Pat. No. 3,692,744.
  • preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and propane and pentaerythritol.
  • polyalkylene terephthalates which have been prepared solely from terephthalic acid and its reactive derivatives (for example its dialkyl esters) and ethylene glycol and / or 1,3-propanediol and / or 1,4-butanediol (polyethylene, polypropylene and polybutylene terephthalate) , as well as mixtures of these polyalkylene terephthalates.
  • terephthalic acid and its reactive derivatives for example its dialkyl esters
  • ethylene glycol and / or 1,3-propanediol and / or 1,4-butanediol polyethylene, polypropylene and polybutylene terephthalate
  • mixtures of polybutylene and polyethylene terephthalate is very particularly preferred.
  • Preferred polyalkylene terephthalates are also copolyesters which are prepared from at least two of the abovementioned acid components and / or from at least two of the abovementioned alcohol components; particularly preferred copolyesters are poly (ethylene glycol / butanediol-1,4) terephthalates.
  • the polyalkylene terephthalates generally have an intrinsic viscosity of approximately 0.4 to 1.5, preferably 0.5 to 1.3, each measured in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C.
  • the compounds already discussed in the description of the polyalkylene terephthalates can be used as aromatic dicarboxylic acids. Mixtures of 5 to 100 mol% of isophthalic acid and 0 to 95 mol% of terephthalic acid are preferred, in particular mixtures of approximately 80% terephthalic acid with 20% isophthalic acid to approximately equivalent mixtures of these two acids.
  • aromatic dihydroxy compounds also used can be described by the following formula (II),
  • Z represents an alkylene or cycloalkylene group with up to 8 carbon atoms, an arylene group with up to 12 carbon atoms, a carbonyl group, an oxygen or sulfur atom, a sulfonyl group or a chemical bond and
  • m has a value from 0 to 2.
  • the compounds can each carry CrCo-alkyl or alkoxy groups and fluorine, chlorine or bromine as substituents on the phenylene units.
  • Representatives of these substances are dihydroxyphenyl, di- (hydroxyphenyl) alkane, di- (hydroxyphenyl) cycloalkane, di- (hydroxyphenyl) sulfide, di- (hydroxyphenyl) ether, di- (hydroxyphenyl) ketone, di- (hydroxyphenyl) sulfoxide, di - (Hydroxyphenyl),, '- Di- (hydroxyphenyl) dialkylbenzene, di- (hydroxyphenyl) sulfone, di- (hydroxybenzoyl) benzene, resorcinol and hydroquinone and their nucleus alkylated or nucleus halogenated derivatives.
  • 2,2-di- (3 ', 5'-dimethyl-4'-hydroxyphenyl) propane 2,2-di- (4'-hydroxyphenyl) propane, 4,4'-dihydroxydiphenylsulfone, 2,2 -Di (3 ', 5-di-chlorodihydroxyphenyl) propane, l, l-di- (4'-hydroxyphenyl) cyclohexane and 3,4'-dihydroxybenzophenone.
  • any mixtures of these and the polyesters mentioned below can also be used.
  • Polyesters are also understood to mean polycarbonates and polyester carbonates.
  • Polycarbonates and polyester carbonates are known from the literature or can be prepared by processes known from the literature (for the production of polycarbonates see, for example, Schnell, “Chemistry and Physics of Polycarbonates", Interscience Publishers,
  • Aromatic polycarbonates are produced e.g. by reacting diphenols with carbonic acid halides, preferably phosgene and / or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalogenides, according to the phase interface method, optionally using chain terminators, for example monophenols and optionally using trifunctional or more than trifunctional branching agents or triphenols, for example triphenols.
  • Diphenols for the preparation of the aromatic polycarbonates and / or aromatic polyester carbonates are preferably those of the formula (III)
  • B are each C 1 -C 12 -alkyl, preferably methyl or halogen, preferably chlorine and / or bromine,
  • R 1 and R 2 can be selected individually for each X 1 , independently of one another hydrogen or Ci-Cö-alkyl, preferably hydrogen, methyl or ethyl,
  • n is an integer from 4 to 7, preferably 4 or 5, with the proviso that at least one atom X 1 R 1 and R 2 are alkyl at the same time,
  • Preferred diphenols are hydroquinone, resocin, dihydroxydiphenols, bis- (hydroxypheny ⁇ ) -C ⁇ -C5-alkanes, bis- (hydroxyphenyl) -C 5 -C 6 -cycloalkanes, bis- (hydroxyphenyl) ethers, bis- ( hydroxyphenyl) sulfoxides, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones and ⁇ , ⁇ -bis (hydroxyphenyl) diisopropyl benzenes and their core-brominated and / or core-chlorinated derivatives.
  • diphenols are 4,4'-dihydroxydiphenyl, bisphenol-A, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis- (4-hydroxyphenyl) -3.3.5-trimethylcyclohexane, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone and their di- and tetrabrominated or chlorinated derivatives such as 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4 -hydroxyphenyl) propane or 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane.
  • 2,2-Bis- (4-hydroxy ⁇ henyl) propane (bisphenol-A) is particularly preferred.
  • the diphenols can be used individually or in any mixtures.
  • the diphenols are known from the literature or can be obtained by processes known from the literature.
  • Chain terminators suitable for the production of the thermoplastic, aromatic polycarbonates are, for example, phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, but also long-chain alkylphenols, such as 4- (1,3-tetramethylbutyl) -phenol according to DE-A 2 842 005 or monoalkylphenol or dialkylphenols with a total of 8 to 20 carbon atoms in the alkyl substituents, such as 3,5-di-tert-butylphenol, p-iso-octylphenol, p-tert.
  • alkylphenols such as 4- (1,3-tetramethylbutyl) -phenol according to DE-A 2 842 005 or monoalkylphenol or dialkylphenols with a total of 8 to 20 carbon atoms in the alkyl substituents, such as 3,5-di-tert-butylphenol, p-iso-octy
  • the amount of chain terminators to be used is generally between 0.5 mol% and 10 mol%, based on the molar sum of the diphenols used in each case.
  • thermoplastic, aromatic polycarbonates have average weight-average molecular weights (M w , measured, for example, by means of an ultracentrifuge or scattered light measurement) of 10,000 to 200,000, preferably 20,000 to 80,000.
  • thermoplastic, aromatic polycarbonates can be branched in a known manner, preferably by incorporating 0.05 to 2.0 mol%, based on the sum of the diphenols used, of trifunctional or more than trifunctional compounds, for example those with three and more phenolic see groups. Both homopolycarbonates and copolycarbonates are suitable.
  • copolycarbonates according to the invention 1 to 25% by weight, preferably 2.5 to 25% by weight (based on the total amount of diphenols to be used) of polydiorganosiloxanes with hydroxy-aryloxy end groups can also be used. These are known (see, for example, US Pat. No. 3,419,634) or according to the literature
  • Process can be produced.
  • the production of polydiorganosiloxane-containing copolycarbonates is e.g. B. described in DE-A 3 334 782.
  • preferred polycarbonates are the copolycarbonates of bisphenol A with up to 15 mol%, based on the molar sum of diphenols, other than the diphenols mentioned as preferred or particularly preferred, in particular 2,2-bis ( 3,5-dibromo-4-hydroxyphenyl) propane.
  • Aromatic dicarboxylic acid dihalides for the production of aromatic polyester carbonates are, for example, the diacid dichlorides of isophthalic acid, terephthalic acid, diphenyl ether-4,4'-dicarboxylic acid and naphthalene-2,6-dicarboxylic acid.
  • Mixtures of the diacid dichlorides of isophthalic acid and terephthalic acid in a ratio between 1:20 and 20: 1 are particularly preferred.
  • a carbonic acid halide preferably phosgene, is additionally used as a bifunctional acid derivative.
  • chain terminators for the production of the aromatic polyester carbonates are their chlorocarbonic acid esters and the acid chlorides of aromatic monocarboxylic acids, which may be substituted by C 1 -C 22 -alkyl groups or by halogen atoms, and aliphatic C 2 -C 22 -Monocarboxylic acid chlorides into consideration.
  • the amount of chain terminators is in each case 0.1 to 10 mol%, based on moles of diphenols in the case of the phenolic chain terminators and on moles of dicarboxylic acid dichlorides in the case of monocarboxylic acid chloride chain terminators.
  • the aromatic polyester carbonates can also contain aromatic hydroxycarboxylic acids as building blocks.
  • the aromatic polyester carbonates can be linear or branched in a known manner (see also DE-A 2 940 024 and DE-A 3 007 934).
  • Trifunctional or polyfunctional carboxylic acid chlorides such as trimesic acid trichloride, cyanuric acid trichloride, 3,3 '-, 4,4'-benzophenone tetracarboxylic acid tetrachloride, 1,4,5,8-naphthalenetetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride, in amounts of 0.01, for example, can be used as branching agents up to 1.0 mol% (based on the dicarboxylic acid dichlorides used) or tri- or polyfunctional phenols, such as phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene-2,4,4 dimethyl-2,4
  • the proportion of carbonate structural units in the thermoplastic, aromatic polyester carbonates can vary as desired.
  • the proportion of carbonate groups is preferably up to 100 mol%, in particular up to 80 mol%, particularly preferably up to 50 mol%, based on the sum of ester groups and carbonate groups.
  • Both the ester and the carbonate content of the aromatic polyester carbonates can be present in the form of blocks or randomly distributed in the polycondensate.
  • the relative solution viscosity ( ⁇ re ⁇ ) of the aromatic polycarbonates and polyester carbonates is in the range from 1.18 to 1.4, preferably from 1.22 to 1.3 (measured on
  • thermoplastic, aromatic polycarbonates and polyester carbonates can be used alone or in any mixture with one another.
  • polyester block copolymers such as. B. copolyether esters as described in US-A 3,651,014.
  • Component B is used for flame-retarding the polyester molding composition
  • the proportion of nitrogen-containing compound B.l is preferably 7 to 13% by weight, particularly preferably 9 to 11% by weight, based on the molding composition.
  • the proportion of the phosphorus-containing compound B.2 is preferably 8 to 13% by weight, particularly preferably 9 to 12% by weight, also based on the molding composition.
  • Suitable nitrogen compounds B1) are melamine cyanurate, melamine, melamine borate, melamine oxalate, melamine phosphate primary, melamine phosphate sec. And melamine pyrophosphate sec., Polymeric melamine phosphate and neopentyl glycol boric acid melamine.
  • guanidine salts such as guanidine carbonate, guanidine cyanurate primary, guanidine phosphate primary, guanidine phosphate sec, guanidine sulfate primary, guanidine sulfate sec, pentaerythritol boric acid guanidine, neopentyl glycol boric acid guanidine, urea phosphate green and urea cyanurate.
  • condensed nitrogen-containing compounds such as melem and melon can also be used.
  • ammonium polyphosphate and tris (hydroxyethyl) isocyanurate or its reaction products with carboxylic acids benzoguanamine and its adducts or salts and its nitrogen-substituted products and their salts and adducts.
  • Allantoin compounds and their salts with phosphoric acid, boric acid or pyrophosphoric acid and glycolurils or their salts are also suitable as further nitrogen-containing components.
  • Inorganic nitrogen-containing compounds such as ammonium salts can also be used.
  • the melamine compounds are preferred.
  • the nitrogen compound melamine cyanurate which is very particularly preferred in the context of the present invention is understood to mean the reaction product from preferably equimolar amounts of melamine and cyanuric acid or isocyanuric acid. This includes all commercially available and commercially available product qualities. Examples include ® 315 (Fa. Budenheim, Budenheim, Germany) and others Melapur ® MC 25 (Messrs. DSM Melapur, Heerlen, Netherlands) and Budit.
  • the melamine cyanurate used consists of particles with average particle diameters from 0.1 ⁇ m to 100 ⁇ m, preferably from 0.1 ⁇ m to 25 ⁇ m, particularly preferably 0.1 ⁇ m to 7 ⁇ m, and can be surface-treated or coated with known agents. These include organic compounds which can be applied to the melamine cyanurate in monomeric, oligomeric and / or polymeric form. For example, coating systems can be used which are based on silicon-containing compounds such as organofunctionalized silanes or organosiloxanes. Coatings with inorganic components are also possible.
  • Melamine cyanurate is usually obtained from the starting materials in an aqueous medium at temperatures between 90 and 100 ° C.
  • the phosphorus compounds B.2) used in the flame retardant are phosphates of the general formula (I)
  • R 1 , R 2 , R 3 and R 4 independently of one another each optionally halogenated C 1 -C 6 -alkyl, in each case optionally C 5 - substituted by alkyl, preferably C 1 -C 4 -alkyl, and / or halogen, preferably chlorine, bromine to Cg-cycloalkyl, Cg- to C 2 o-aryl or C 7 - to Ci 2 -aralkyl, very preferably phenyl,
  • n independently of one another, 0 or 1
  • N is 0 to 50, preferably 0 to 20, particularly preferably 0 to 10, in particular 0 to 6,
  • X is a mono- or polynuclear aromatic radical having 6 to 30 carbon atoms, derived from diphenols, is preferred.
  • R 1, R 2, R 3 and R 4 are independently C ⁇ -C 4 alkyl, phenyl, naphthyl or phenyl-C 1 -C 4 alkyl.
  • the aromatic groups R 1 , R 2 , R 3 and R 4 can in turn be substituted with halogen and / or alkyl groups, preferably chlorine, bromine and / or -CC 4 alkyl.
  • Particularly preferred aryl radicals are cresyl, phenyl, xylenyl, propylphenyl or butylphenyl.
  • Monophosphorus compounds of the formula (I) are in particular tributyl phosphate
  • triphenyl phosphate is particularly preferred.
  • Another preferred phosphorus compound is bisphenol A bisphenyl diphosphate.
  • the phosphorus compounds mentioned are known (cf. e.g. EP-A 363 608, EP-A 640 655) or can be prepared in an analogous manner by known methods
  • the polyolefin compound used as component C) is a
  • Polyolefin wax preferably around a polypropylene or polyethylene wax, of which polyethylene waxes are again particularly preferred.
  • a polyolefin wax is generally understood to mean polyolefins with a wax-like character. Such compounds can be obtained by processes known to those skilled in the art, either by direct polymerization of olefinic base monomers or by targeted ones
  • the polyolefin compound is used in amounts of 0.05 to 1.5% by weight, preferably 0.1 to 0.7% by weight, particularly preferably 0.15 to 0.45% by weight. Mixtures of different polyolefins can also be used. If zinc sulfide is used as component D), this is done in amounts of preferably 0.1 to 4% by weight, particularly preferably 0.4 to 3.5% by weight, based on the total molding composition. In certain embodiments of the present invention, the use of 0.4 to 1.0% by weight of ZnS is particularly preferred.
  • the zinc sulfide is usually used as a particulate solid.
  • Sachtolith ® HDS or Sachtolith ® HD (both from Sachtleben, Duisburg, Germany). It is also possible to use compacted material and masterbatches in a polymeric carrier material.
  • the zinc sulfide can be surface-treated or coated with known agents. These include organic compounds that can be applied in monomeric, oligomeric and / or polymeric form. Coatings with inorganic components are also possible.
  • coating systems can be used which are based on silicon-containing compounds such as organofunctionalized silanes, aminosilanes or
  • Organosiloxanes are based.
  • the molding composition contains, as component E), 0 to 50% by weight, preferably 10 to 40, in particular 10 to 35% by weight of fillers and reinforcing materials.
  • glass fibers, glass balls, glass fabrics, glass mats, carbon fibers, aramid fibers, potassium titanate fibers, natural fibers, amorphous silica, magnesium carbonate, barium sulfate, feldspar, mica, silicates, quartz, talc, kaolin, Titanium dioxide, wollastonite, etc. can be added, which can also be surface-treated.
  • Preferred reinforcing materials are commercially available glass fibers.
  • the glass fibers which generally have a fiber diameter between 8 and 18 ⁇ m, can be added as continuous fibers or as cut or ground glass fibers, it being possible for the fibers to be equipped with a suitable sizing system and an adhesion promoter or adhesion promoter system, for example based on silane.
  • Acicular mineral fillers are also suitable.
  • acicular mineral fillers are understood to be mineral fillers with a pronounced acicular character.
  • An example is needle-shaped wollastonite.
  • the mineral preferably has an L / D (length / diameter ratio of 8: 1 to 35: 1, preferably from 8: 1 to 11: 1).
  • the mineral filler can optionally be surface-treated.
  • rubber-elastic polymers (often also referred to as impact modifier, elastomer or rubber) can prove advantageous in some cases with regard to the mechanical property profile.
  • these are copolymers which are preferably composed of at least two of the following monomers: ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile and acrylic or methacrylic acid esters with 1 to 18 carbon atoms in the alcohol component.
  • Rubber-elastic polymers such as are described in WO 00/46419 are preferred.
  • polyesters according to the invention can also contain other additives, such as agents against heat decomposition, agents against heat crosslinking, agents against damage by ultraviolet light, plasticizers, flow and processing aids, flame retardants, lubricants and mold release agents, Contain nucleating agents, antistatic agents, stabilizers as well as dyes and pigments.
  • S is explicitly excluded as component F.
  • oxidation retarders and heat stabilizers are sterically hindered phenols and / or phosphites, hydroquinones, aromatic secondary ones
  • Amines such as diphenylamines, various substituted representatives of these groups and mixtures thereof.
  • UV stabilizers Various substituted resorcinols, salicylates, benzotriazoles and benzophenones may be mentioned as UV stabilizers.
  • Inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide and carbon black, organic pigments such as phthalocyanines, quinacridones, perylenes and dyes such as nigrosine and anthraquinones can also be added as colorants and other colorants.
  • nucleating agents e.g. Sodium phenyl phosphinate, aluminum oxide, silicon dioxide and preferably talc are used.
  • preferably halogen-free phosphorus compounds not specifically mentioned here can also be used alone or in any combination with other preferably halogen-free phosphorus compounds.
  • This also includes purely inorganic phosphorus compounds such as boron phosphate hydrate or elemental phosphorus, preferably red phosphorus.
  • lubricants and mold release agents are ester waxes, pentaerythritol tetrastearate (PETS), long-chain fatty acids (eg stearic acid or behenic acid), their salts (eg Ca or Zn stearate) as well as amide derivatives (eg ethylene-bis-stearylamide) or montan waxes (Mixtures of straight-chain, saturated carboxylic acids with chain lengths of 28 to 32 carbon atoms.
  • PETS pentaerythritol tetrastearate
  • long-chain fatty acids eg stearic acid or behenic acid
  • their salts eg Ca or Zn stearate
  • amide derivatives eg ethylene-bis-stearylamide
  • montan waxes Mentures of straight-chain, saturated carboxylic acids with chain lengths of 28 to 32 carbon atoms.
  • plasticizers are phthalic acid dioctyl ester, phthalic acid dibenzyl ester, phthalic acid butyl benzyl ester, hydrocarbon oils, N- (n-butyl) benzenesulfonamide.
  • Component A / l PBT Pocan® B 1300 00/000 (Bayer AG, Leverkusen, Germany)
  • Component A / 2 PBT Pocan® B 1600 (Bayer AG, Leverkusen, Germany)
  • Component A / 3 PET RIO (Agfa, Mortsel, Belgium)
  • Component B.l Melamine cyanurate (Melapur® MC 25, DSM-Melapur, Heerlen, Holland)
  • Component B.2 triphenyl phosphate (Disflamoll® TP, Bayer AG, Leverkusen, Germany)
  • Component C polyolefin wax Luwax® A (from BASF AG, Ludwigshafen, Germany)
  • Component D ZnS (Sachtolith® HDS, Sachtleben, Duisburg, Germany)
  • Component E / l chopped glass fiber (CS 7962, Bayer AG, Leverkusen, Germany)
  • Additive F3 stabilizer 10% concentrate in Pocan ® B 1300 00/000 (Bayer AG, Leverkusen, Germany)
  • the individual components are mixed in the specified ratios in a twin-screw extruder of the type Werner & Pfleiderer from Werner & Pfleiderer at temperatures of 260 ° C., discharged as a strand, cooled to granulation capacity and granulated. After drying, the granulate is processed at temperatures of 260 ° C into standard test specimens, on which the mechanical, electrical and fire properties are determined.
  • the flame retardancy of plastics is determined according to the UL94V method (see a) Underwriters Laboratories Inc. Standard of Safety, "Test for Flammability of Plastic Materials for Parts in Devices and Appliances", S14 ff, Northbrook 1998; b) J. Troitzsch, "International Plastics Flammability Handbook", p. 346 ff., Hanser Verlag, Kunststoff 1990). Afterburning times and
  • the UL94V-1 classification requires that the individual afterburning times are not longer than 30 seconds and that the sum of the afterburning times of 10 flame treatments of 5 samples is not greater than 250 seconds. The total afterglow time must not exceed 250 seconds. The other criteria are identical to those mentioned above.
  • a classification in the fire class UL94V-2 occurs if there is a burning drip if the other criteria of the UL94V-1 classification are met.
  • the mechanical properties of the polymer compounds are determined by means of the tensile test according to ISO 527 (testing on shoulder bars) and the bending test
  • test results shown in the table above demonstrate that the molding compositions according to the invention have high impact strength and edge fiber elongation in addition to the desired flame resistance, whereas comparative examples 1 and 2 also show significantly poorer mechanical properties if the flame resistance is insufficient.
  • ZnS see Examples 2 and 3
  • the appealing mechanical level of the molding compositions according to the invention can be increased even further.

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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)
  • Artificial Filaments (AREA)
EP02745385A 2001-06-27 2002-06-14 Flammwidrige polyesterformmassen mit polyolefinadditiven Withdrawn EP1409587A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10130832A DE10130832A1 (de) 2001-06-27 2001-06-27 Flammwidrige Polyesterformmassen mit Polyolefinadditiven
DE10130832 2001-06-27
PCT/EP2002/006554 WO2003002664A1 (de) 2001-06-27 2002-06-14 Flammwidrige polyesterformmassen mit polyolefinadditiven

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EP1409587A1 true EP1409587A1 (de) 2004-04-21

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US (1) US20030083409A1 (enrdf_load_stackoverflow)
EP (1) EP1409587A1 (enrdf_load_stackoverflow)
JP (1) JP2004530787A (enrdf_load_stackoverflow)
KR (1) KR20040022435A (enrdf_load_stackoverflow)
CN (1) CN1538992A (enrdf_load_stackoverflow)
BR (1) BR0210615A (enrdf_load_stackoverflow)
CA (1) CA2451470A1 (enrdf_load_stackoverflow)
DE (1) DE10130832A1 (enrdf_load_stackoverflow)
MX (1) MXPA03011402A (enrdf_load_stackoverflow)
WO (1) WO2003002664A1 (enrdf_load_stackoverflow)
ZA (1) ZA200309855B (enrdf_load_stackoverflow)

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FR2864098B1 (fr) * 2003-12-19 2007-08-31 Rhodia Chimie Sa Systeme ignifugeant a base de composes du phosphore et composition polymerique ignifugee
US20060100330A1 (en) * 2004-11-10 2006-05-11 Natarajan Kavilipalayam M Composition for use in forming an article
US7375167B2 (en) * 2005-05-09 2008-05-20 Basf Se Hydrolysis-resistance composition
WO2007112995A1 (en) * 2006-04-04 2007-10-11 Dsm Ip Assets B.V. Halogen free flame retardant polyester composition
DE102008041918A1 (de) * 2008-09-09 2010-03-11 Evonik Degussa Gmbh Silanolkondensationskatalysatoren zur Vernetzung von gefüllten und ungefüllten Polymer-Compounds
KR101291469B1 (ko) * 2009-12-29 2013-07-30 주식회사 삼양사 난연성 폴리에틸렌테레프탈레이트 수지 조성물
US8604105B2 (en) 2010-09-03 2013-12-10 Eastman Chemical Company Flame retardant copolyester compositions
CN110029406A (zh) * 2010-11-17 2019-07-19 Frx 聚合物股份有限公司 作为用于聚酯纤维的阻燃剂的膦酸酯聚合物、共聚物及其各自的寡聚物
EP2511337A1 (de) * 2011-04-15 2012-10-17 Basf Se Flammhemmende thermoplastische Formmasse
CN115135719B (zh) * 2020-02-19 2024-01-19 东洋纺Mc株式会社 阻燃性聚酯树脂组合物以及含有其的模制品
CN115651315A (zh) * 2022-11-22 2023-01-31 四川帕沃可矿物纤维制品集团有限公司 一种玄武岩纤维增强的注塑用改性聚丙烯材料

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Publication number Publication date
DE10130832A1 (de) 2003-01-16
MXPA03011402A (es) 2004-07-01
US20030083409A1 (en) 2003-05-01
BR0210615A (pt) 2004-08-10
CN1538992A (zh) 2004-10-20
CA2451470A1 (en) 2003-01-09
JP2004530787A (ja) 2004-10-07
ZA200309855B (en) 2005-04-25
KR20040022435A (ko) 2004-03-12
WO2003002664A1 (de) 2003-01-09

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