EP1137711A1 - Matieres moulables ininflammables a base de polycarbonate exemptes de chlore et de brome - Google Patents

Matieres moulables ininflammables a base de polycarbonate exemptes de chlore et de brome

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Publication number
EP1137711A1
EP1137711A1 EP99972236A EP99972236A EP1137711A1 EP 1137711 A1 EP1137711 A1 EP 1137711A1 EP 99972236 A EP99972236 A EP 99972236A EP 99972236 A EP99972236 A EP 99972236A EP 1137711 A1 EP1137711 A1 EP 1137711A1
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EP
European Patent Office
Prior art keywords
weight
acid
compositions according
molding compositions
polycarbonate
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.)
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Application number
EP99972236A
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German (de)
English (en)
Inventor
Wolfgang Ebert
Knud Reuter
Klaus Horn
Thomas Fritz
Klaus Berg
Dirk Jahn
Ralf Hufen
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Bayer AG
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Bayer AG
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Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP1137711A1 publication Critical patent/EP1137711A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • 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
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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
    • C08L25/08—Copolymers of styrene
    • C08L25/14—Copolymers of styrene with unsaturated esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • 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

Definitions

  • the present invention relates to glass fiber-reinforced, flame-retardant polycarbonate molding compositions with flame retardants containing epoxy groups, optionally in addition to other flame retardants, antidripping agents and other additives customary for polycarbonate.
  • Flame retardants for glass fiber reinforced polycarbonates are described in large numbers in patents and publications.
  • aromatic sulfonic acid salts is described in US Pat. Nos. 3,933,734 and 3,940,366.
  • the disadvantage of this flame retardant is that fire class V-0 is not always achieved with thin rods and that the additives as ionic salts tend to catalyze transesterification and degradation reactions in polycarbonate.
  • alkali salts for the production of flame-retardant polycarbonates has long been known (see for example DE-OS 1 930 257 and US-A 3 775 367, DE-OS 2 049 358 and US-A 3 836 490, DE-OS 2 149 31 1 and GB-PS 1 370 744).
  • DE-OS 25 35 261 discloses the production of flame-retardant polycarbonates, to which organic alkali metal salts or organic alkaline earth metal salts or mixtures thereof are added in combination with siloxanes. Flame-retardant polycarbonates also emerge from EP-A 392 252; Both alkali and alkaline earth salts and siloxanes serve as fire protection additives.
  • oligomeric or polymeric siloxanes described there lead to severe intolerances even in the smallest dosage.
  • volatile, cyclic siloxanes are formed in the finished part by cleavage, which can lead to contact damage in electrical devices.
  • flame retardant polycarbonates which contain organic alkali metal salts, organic alkaline earth metal salts or their mixtures and alkali metal or alkaline earth metal halides or organic halides. It can also contain a siloxane that improves flame retardancy.
  • oligomeric and polymeric siloxanes described there only work in combination with an organic halide; in combination with a salt alone, they lead to a deterioration in the fire properties.
  • DE-OS 29 18 882 and DE-OS 29 18 883 describe flame-retardant thermoplastic mixtures which contain organic halogen compounds, alkali metal or alkaline earth metal salts and an anti-drip agent.
  • JP-A 60/149658 discloses polycarbonate resins which contain potassium phosphates, aromatic phosphites, silicon compounds and glass fibers.
  • the polycarbonates have improved flame retardancy.
  • CH Si (O-nonyl) 3 is mentioned as the silicon compound.
  • JP-A 60/186559 discloses polycarbonate resins which contain potassium phosphonates, aromatic phosphites, 4,4-dihydroxydiphenylalkane oligomers and organic silicon compounds.
  • the polycarbonate resins are flame retardant.
  • Methyl tri (sec) octyloxysilane, tetranonyl silicate and tetridecyl silicate are mentioned as silicon compounds.
  • transesterification catalysts especially phosphites
  • they have an adverse effect on polycarbonates.
  • they cause a deterioration in hydrolysis resistance and in electrical applications can lead to contact damage due to the release of phosphoric acids.
  • the silicon compounds described which are characterized by a methyl radical bonded to the silicon and large alkoxy radicals, also have further disadvantages such as
  • halogenated phthalimides described in US Pat. No. 5,326,800 produces reliable fire protection, but has the disadvantage of containing halogen and therefore developing corrosive gases in the event of a fire; this also applies to the sole use of halogenated phthalimides described in JP-A 75/1 19041, and the method of using organic alkali metal salts in addition to organic halides described in DE-OS 27 44 016 and US-A 4 1 10 299.
  • the task was therefore to develop a chlorine- or bromine-free flame retardant for glass fiber reinforced polycarbonate molding compounds.
  • epoxy-containing compounds as flame retardants, optionally in addition to ahphatic or aromatic organic salts, in particular sulfonic acid salts.
  • the present invention therefore relates to flame-retardant polycarbonate molding compositions
  • the molding compositions according to the invention can contain additives such as thermal stabilizers, UV stabilizers, antioxidants, mold release agents, other flame retardants, antidripping agents, pigments or fillers in the amounts customary for thermoplastic polycarbonates, and also other polymers as blend partners, for example ABS, SAN, EPDM or polyester, in particular those based on terephthalic acid.
  • additives such as thermal stabilizers, UV stabilizers, antioxidants, mold release agents, other flame retardants, antidripping agents, pigments or fillers in the amounts customary for thermoplastic polycarbonates, and also other polymers as blend partners, for example ABS, SAN, EPDM or polyester, in particular those based on terephthalic acid.
  • Aromatic (co) polycarbonates a) for the purposes of the present invention are both homopolycarbonates and copolycarbonates; which can be linear or branched in a known manner.
  • polycarbonates to be used according to the invention are produced in a known manner from diphenols, carbonic acid derivatives, optionally chain terminators and optionally branching agents, with part of the carbonic acid derivatives being replaced by aromatic dicarboxylic acids or derivatives of dicarboxylic acids in order to produce polyester carbonates.
  • aromatic polycarbonates including the thermoplastic, aromatic
  • Polyester carbonates have average molecular weights M. (determined by measuring the relative viscosity at 25 ° C. in CH 2 C1 2 and a concentration of 0.5 g per 100 ml of CH 2 C1 2 ) from 12,000 to 120,000, preferably from 15,000 up to 80,000 and in particular from 22,000 to 60,000.
  • Diphenols suitable for the preparation of the polycarbonates to be used according to the invention are, for example, hydroquinone, resorcinol, dihydroxydiphenyl, bis (hydroxyaryl) alkanes, bis (hydroxyaryl) cycloalkanes, bis (hydroxyaryl) sulfides, bis (hydroxyaryl) ethers, bis (hydroxyaryl) - ketones, bis (hydroxyaryl) sulfones, bis (hydroxyaryl) sulfoxides, ( ⁇ , ⁇ '-bis (hydroxyaryl) diisopropylbenzenes, and also their ring-alkylated and ring-halogenated compounds.
  • Preferred diphenols are 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) -l-phenyl-propane, l, l-bis (4-hydroxyphenyl) phenylethane, 2,2-bis (4-hydroxyphenyl) - propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, l, l-bis (4-hydroxyphenyl) -m / p-diisopropylbenzene, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, Bis (3,5-dimethyl-4-hydroxyphenyl) methane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 2, 4-bis (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane, l, l-bis (3,5-dimethyl-4-hydroxyphenyl) -m / p
  • diphenols are 4,4'-dihydroxydiphenyl, l, l-bis- (4-hydroxyphenyl) phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl- 4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.
  • Suitable chain terminators are both monophenols and monocarboxylic acids.
  • Suitable monophenols are phenol, alkylphenols such as cresols, p-tert-butylphenol, p-n-octylphenol, p-iso-octylphenol, p-n-nonylphenol and p-iso-nonylphenol,
  • Halophenols such as p-chlorophenol, 2,4-dichlorophenol, p-bromophenol and 2,4,6-tribromophenol or mixtures thereof.
  • Suitable monocarboxylic acids are benzoic acid, alkylbenzoic acids and halobenzoic acids.
  • Preferred chain terminators are the phenols of the formula (V)
  • R 3 is H or a branched or unbranched C, -C
  • the amount of chain terminator to be used is 0.5 mol% to 10 mol%, based on moles of diphenols used in each case.
  • the chain terminators can be added before, during or after phosgenation.
  • Suitable branching agents are the trifunctional or trifunctional compounds known in polycarbonate chemistry, in particular those having three or more than three phenolic OH groups.
  • Suitable branching agents are, for example, phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) hepten-2, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 1, 3,5-tri- (4-hydroxyphenyl) benzene, 1,1,1-tri (4-hydroxyphenyl) ethane, tri (4-hydroxyphenyl) phenylmethane, 2,2-bis- [4,4-bis (4th -hydroxyphenyl) cyclohexyl] propane, 2,4-bis (4-hydroxyphenylisopropyl) phenol, 2,6-bis (2-hydroxy-5'-methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenyl) - 2- (2,4-dihydroxyphenyl) propane.
  • the amount of branching agents which may be used is 0.05 mol% to 2.5 mol%, based in turn on moles of diphenols used in each case.
  • the branching agents can either be introduced with the diphenols and the chain terminators in the aqueous alkaline phase, or added dissolved in an organic solvent before the phosgenation.
  • Aromatic dicarboxylic acids suitable for the production of polyester carbonates are, for example, phthalic acid, terephthalic acid, isophthalic acid, tert-butylisophthalic acid, 3,3'-diphenyldicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4-benzophenone dicarboxylic acid, 3,4'- Benzophenone dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenyl sulfone dicarboxylic acid, 2,2-bis (4-carboxyphenyl) propane, trimethyl-3-phenyl indane-4,5'-dicarboxylic acid.
  • aromatic dicarboxylic acids terephthalic acid and / or isophthalic acid are particularly preferably used.
  • Dicarboxylic acids are the dicarboxylic acid dihalides and the dicarboxylic acid dialkyl esters, in particular the dicarboxylic acid dichlorides and the dicarboxylic acid dimethyl esters.
  • Preferred methods of producing the (co) polycarbonates to be used according to the invention are the interfacial process and the melt transesterification process.
  • phosgene is preferably used as the carbonic acid derivative, in the latter case preferably diphenyl carbonate.
  • Catalysts, solvents, work-up, reaction conditions etc. for the (co) polycarbonate production are sufficiently described and known in both cases.
  • glass fibers b A large number of commercially available glass fiber types and types are suitable as glass fibers b), that is to say cut long glass fibers ("chopped strands") and short glass fibers (“milled fibers”), provided that they are made compatible with polycarbonate by suitable sizes.
  • Glass fibers made of E-glass are preferably used to produce the molding compositions according to the invention.
  • e-glass is an aluminum-boron-silicate glass with an alkali oxide content of ⁇ 1% by weight. Glass fibers with a diameter of 8 to 20 ⁇ m and a length of 3 to 6 mm (“chopped strands”) are preferably used;
  • short glass fibers (“milled fibers”) can also be used, as can suitable glass balls.
  • Glass fibers with a diameter of 10 to 17 ⁇ m and a length of 4 to 5 mm are particularly preferably used.
  • Preferred (co) polymers c) are those which can be obtained by (co) polymerizing (1) 1-100% by weight, preferably 5-80% by weight, particularly preferably 10-60% by weight, of glycidyl acrylate or glycidyl methacrylate or mixtures thereof, glycidyl methacrylate being preferred, and
  • RC -C 24 alkyl, C 7 -C 24 alkaryl or aralkyl (optionally substituted or halogenated), C 6 -C 24 aryl or glycidyl (optionally substituted or halogenated), preferably methyl, butyl or glycidyl,
  • R represents H or methyl
  • R 2 is C 7 -C 24 alkaryl or aralkyl or C 6 -C 24 aryl (optionally substituted or halogenated), preferably phenyl, and
  • RC -C 24 alkyl, C 7 -C 24 alkaryl or aralkyl or C 6 -C 24 aryl (optionally substituted or halogenated), C 2 -C 24 acyl, preferably ethyl or acetyl, with the proviso that 1 to 100 mol%, preferably 5 to 80 mol%, particularly preferably 10 to 60 mol% of the structural units of the formula (I) contained in the (co) polymers are glycidyl esters.
  • a (co) polymer can contain several different structural elements of each of types (I), (II) or (III).
  • the (co) polymers c) are very particularly preferably prepared by copolymerizing a mixture of
  • glycidyl methacrylate, methyl methacrylate, butyl methacrylate and styrene can be used, for example, as (co) polymeric c) copolymers.
  • Such copolymers are commercially available.
  • the company Anderson (Adrian, Michigan, USA) produces copolymers of this type with a content of approximately 27% by weight of glycidyl methacrylate under the trade name Almatex® PD-7610 and
  • Copolymers with a content of approx. 40% by weight glycidyl methacrylate are sold under the trade name Almatex ® AP-3402.
  • epoxy group-containing carboxylic acid esters c preference is given to using compounds which have carboxylic acid residues with 5-36 C atoms, preferably 10-25 C atoms, and residues which are derived from mono- or polyhydric alcohols with 2-25 C- Derive atoms.
  • residues which are derived from monohydric alcohols those with 4-35 C atoms, in particular those with 9-24 C atoms, are preferred as residues which are derived from polyhydric alcohols, those of diols, triols or tetrols with 2 up to 20 carbon atoms, preferably 2-5 carbon atoms. Both fully and partially esterified residues of polyhydric alcohols can be contained in the carboxylic acid esters c).
  • the carboxylic acid esters c) contain epoxy groups, at least one epoxy group being present per molecule.
  • the epoxy groups can be contained in both the fatty acid and alcohol residues.
  • the fatty acid residues can also contain hydroxyl groups.
  • Examples of carboxylic acid residues occurring in the carboxylic acid esters c) according to the invention are those which are derived from formic acid, acetic acid, n- or i-propionic acid, n- or i-butyric acid, n- or i-valeric acid, carpronic acid, oenanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tri-, decanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, Melissinklareklare, acrylic acid, crotonic acid, palmitoleic acid, oleic acid, erucic acid, sorbic acid, linoleic acid, linolenic acid, Elaeostearic acid, arachid
  • residues of alcohols which occur in the carboxylic acid esters c) according to the invention are those which are derived from alcohols which can be obtained by hydrogenating the carboxylic acids mentioned, in addition to those which are derived from methanol, ethanol, n- or i-propanol, n - or i-butanol, n- or i-pentanol, hexanols, heptanols, octanols, nonanols, decanol, undecanol, lauryl alcohol, tridecanol, myristyl alcohol, pentadecanols, cetyl alcohol, heptadecanols, stearyl alcohol, oleyl alcohol, erucyl alcohol, ricinol alcohol, ricinol alcohol, ricinol alcohol, ricinol alcohol,
  • Linolenyl alcohol nonadecanol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol, glycerin, trimethylolpropane, pentaerythritol or mixtures thereof.
  • the double bonds contained in the carboxylic acid esters c) are preferably epoxidized up to a remaining iodine number of at most 50, preferably at most 20, particularly preferably at most 5. If more than one epoxide group is present in the molecule, the epoxide groups can be partially hydrolyzed to diols, but must at least one non-hydrolyzed epoxy group per molecule.
  • Products which can be obtained by epoxidation of natural unsaturated glycerides are particularly preferably used as carboxylic acid esters c).
  • Examples include epoxidized linseed oil or epoxidized soybean oil.
  • Such products are commercially available, for example under the trade names EDENOL ® (epoxidized fatty acid ester) or SOVERMOL ® (epoxidized, diol-containing fatty acid ester)
  • the (co) polyethers c) which have epoxy end groups can have aliphatic, araliphatic or aromatic structural units. As a rule, the units will contain 1 to 40 carbon atoms.
  • the (co) polyethers c) can also contain different structural units in statistical or blockwise order.
  • a preferred group of polyethers has alkylidene groups with 2 to 18 carbon atoms, in particular structural units containing 2 to 6 carbon atoms.
  • Examples include polyethers with methylidene, ethylidene, i- or n-propylidene, i- or n- or neo-butylidene, pentylidene, hexylidene, hexylethylidene, dodecanylidene or
  • Dexadecanylidic units Another preferred group of polyethers are those which are prepared using branching agents such as triols, tetrols and pentols as the starting molecule, glycerol, trimethylolpropane and pentaerythritol in particular being preferred monomers. These branched polyethers then have more than two end groups per molecule.
  • the end groups of the (co) polyether c) which can be used according to the invention can contain OH groups or O-alkyl, O-alkaryl or O-aralkyl, O-aryl or O-acyl radicals having 1 to 40 C atoms, preferably 1 to 25 carbon atoms. End groups which are derived from natural fatty acids or fatty alcohols are particularly preferred, and glycidyl end groups are very particularly preferred.
  • Suitable end groups are those which are derived from acids such as formic acid, acetic acid, n- or i-propionic acid, n- or i-butyric acid, n- or i-valeric acid, carpronic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic tinklare, margaric acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, Melissinklareklare, acrylic acid, crotonic acid, palmitoleic acid, oleic acid, erucic acid, sorbic acid, linoleic acid, linolenic acid, Elaeo- stearic acid, arachidonic acid, Clupanodonic acid, docos
  • (co) polyethers which have end groups which are derived from unsaturated alcohols or carboxylic acids, their double bonds are epoxidized up to a remaining iodine number of at most 50, preferably at most 20, particularly preferably at most 5.
  • the (co) polyether c) have on average at least one end group with an epoxy function per molecule.
  • (Co) polyethers are preferably used, all of whose end groups have epoxy functions.
  • the (co) polyethers c) which can be used according to the invention generally have average molecular weights (number average) M n of 100 to 10,000 g / mol.
  • (Co) polyethers with average molecular weights M n of 200 to 5000 g / mol are preferably used, particularly preferably those with average molecular weights M n of 300 to 3000 g / mol.
  • the (co) polyethers c) according to the invention are commercially available or can be obtained by standard reactions familiar to the person skilled in the art.
  • the salts of organic sulfonic acids d) used according to the invention as additional flame retardants preferably correspond to the general formula (IV)
  • R is an optionally fluorinated C, -C 24 alkyl, C 7 -C 2 alkaryl or aralkyl, or C 6 -C 24 aryl radical and
  • Z is Li, Na, K or NH 4, preferably Na or K.
  • salts of organic sulfonic acids d) are: sodium or potassium perfluorobutane sulfonate, sodium or potassium perfluoromethane sulfonate, sodium or potassium diphenyl sulfone sulfonate, sodium or potassium 2-formylbenzenesulfonate, sodium or potassium (N-benzenesulfonyl) benzenesulfonamide.
  • Sodium or potassium perfluorobutane sulfonate is particularly preferably used.
  • the salts of organic sulfonic acids d) can of course also be used in combination with salts of other organic or inorganic acids.
  • examples of such salts are sodium or potassium methylphosphonate, sodium or potassium (2-phenylethylene) phosphonate, lithium phenylphosphonate, trisodium or tripotassium hexafluoroaluminate, disodium or dipotassium hexafluorotitanate, disodium or dipotassium hexafluorosilicate, disodium or dipotassium hexafluorozirconate, sodium or potassium tetrafluoroborate, sodium or potassium hexafluorophosphate, sodium or potassium pyrophosphate, sodium or potassium metaphosphate, lithium or sodium or potassium phosphate.
  • the present invention also relates to a process for the preparation of the molding compositions according to the invention, in which the components of the molding compositions according to the invention and, if appropriate, further additives are mixed either simultaneously or successively, either in bulk or in solution, and then the mixtures either at temperatures between 260 ° C. and 360 ° C melt compounded or melt extruded at temperatures between 250 ° C and 320 ° C.
  • the molding compositions according to the invention can also be prepared in solution by the (co) polycarbonates a), dissolved in a solvent for polycarbonate, simultaneously or successively with the other components b), c) and d ) and optionally other additives are mixed and the solvent is then removed (for example by evaporating the polycarbonate solution) and the mixture obtained is granulated.
  • the molding compositions according to the invention can be processed to flame-retardant moldings on the customary processing machines by known methods under the processing parameters customary for polycarbonate.
  • the molding compositions are particularly suitable for injection molding and extrusion articles which have to meet increased requirements with regard to flame resistance.
  • Examples of such shaped bodies are foils, plates, hollow chamber plates, lights, housings for electrical devices or the like.
  • the molded parts are used in a wide variety of areas, for example in the electrical, electronics, lighting, computer, construction, vehicle and / or aircraft sectors. Examples
  • the amounts in the examples relate to the weight of the total mixture.
  • test bars each were then subjected to a flammability test in accordance with UL 94 (flammability of solid plastic samples, Underwriter Laboratories).
  • Example 1 is a comparison test with halogen-containing flame retardant
  • Polymer A glycidyl methacrylate / methyl methacrylate / butyl methacrylate / styrene
  • Polymer B glycidyl methacrylate / methyl methacrylate / butyl methacrylate / styrene copolymer with approx. 40% by weight glycidyl methacrylate (Almatex ® AP-
  • Example 1 is a comparison test with halogen-containing flame protection
  • Polymer A glycidyl methacrylate / methyl methacrylate / butyl methacrylate / styrene
  • Polymer B glycidyl methacrylate methyl methacrylate / butyl methacrylate / styrene copolymer with approx. 40% by weight glycidyl methacrylate (Almatex® AP-
  • Example 1 is a comparison test with halogen-containing flame retardant
  • Ester A epoxidized fatty acid 2-ethylhexyl ester, Edenol B 35 ®, Henkel KGaA, D-40191 Dusseldorf
  • Ester B epoxidized linseed oil, Edenol®B 316, Henkel KGaA, D-40191 Düsseldorf
  • Ester C epoxidized soybean oil, Edenol®D 16, Henkel KGaA, D-40191 Düsseldorf
  • Ester A epoxidized 2-ethylhexyl fatty acid, Edenol®B 35, Henkel KGaA, D-40191 Düsseldorf
  • Ester B epoxidized linseed oil, Edenol®B 316, Henkel KGaA, D-40191 Düsseldorf
  • Ester C epoxidized soybean oil, Edenol D 16 ®, Henkel KGaA, D-40191 Dusseldorf Examples C1 to C9
  • test specimens with the dimensions 127 ⁇ 12 mm. 10 test bars each were then subjected to a flammability test in accordance with UL 94 (flammability of solid plastic samples, Underwriter Laboratories).
  • Example 1 is a comparison test with halogen-containing 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)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

Matières moulables ininflammables et renforcées par des fibres de verre, à base de polycarbonate, qui contiennent des agents ignifugeants refermant des groupes époxyde, le cas échéant en plus d'autres agents ignifugeants, agents anti-dégouttement et autres additifs courants pour le polycarbonate.
EP99972236A 1998-11-13 1999-11-02 Matieres moulables ininflammables a base de polycarbonate exemptes de chlore et de brome Withdrawn EP1137711A1 (fr)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
DE19852404 1998-11-13
DE19852404 1998-11-13
DE19852406 1998-11-13
DE19852405 1998-11-13
DE19852405 1998-11-13
DE19852406 1998-11-13
PCT/EP1999/008357 WO2000029483A1 (fr) 1998-11-13 1999-11-02 Matieres moulables ininflammables a base de polycarbonate exemptes de chlore et de brome

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EP1137711A1 true EP1137711A1 (fr) 2001-10-04

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EP99972236A Withdrawn EP1137711A1 (fr) 1998-11-13 1999-11-02 Matieres moulables ininflammables a base de polycarbonate exemptes de chlore et de brome

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EP (1) EP1137711A1 (fr)
JP (1) JP2002530458A (fr)
KR (1) KR20010082298A (fr)
CN (1) CN1326487A (fr)
AU (1) AU1159000A (fr)
BR (1) BR9915318A (fr)
WO (1) WO2000029483A1 (fr)

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US20050038145A1 (en) * 2003-08-11 2005-02-17 General Electric Company Flame retardant fiber reinforced composition with improved flow
CN100516125C (zh) * 2002-12-16 2009-07-22 沙伯基础创新塑料知识产权有限公司 阻燃的玻璃填充的聚碳酸酯的制造方法及相关的组合物
US7728059B2 (en) * 2006-02-14 2010-06-01 Sabic Innovative Plastics Ip B.V. Polycarbonate compositions and articles formed therefrom
CN102181139B (zh) * 2011-01-27 2013-12-11 上海锦湖日丽塑料有限公司 玻璃纤维增强聚碳酸酯树脂及其制备方法
MX2020004390A (es) 2017-10-27 2020-08-20 Ocv Intellectual Capital Llc Composiciones de encolado que incluyen sales de anion de debilmente coordinante y usos de las mismas.
KR102007099B1 (ko) * 2017-12-28 2019-08-02 롯데첨단소재(주) 열가소성 수지 조성물 및 이로부터 형성된 성형품
WO2021121864A1 (fr) * 2019-12-17 2021-06-24 Covestro Intellectual Property Gmbh & Co. Kg Compositions de polycarbonate contenant des charges et des groupes époxydes contenant du triacylglycérol

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US3839247A (en) * 1973-01-05 1974-10-01 Gen Electric Water-clear hydrolytically stable polycarbonate composition containing an aromatic or aliphatic epoxy stabilizer
US4197232A (en) * 1974-08-09 1980-04-08 General Electric Company Flame retardant polycarbonate composition
DE3041298A1 (de) * 1979-11-08 1981-05-21 General Electric Co., Schenectady, N.Y. Polycarbonat-zubereitung mit verbesserter hydrolytischer stabilitaet
GB2165253A (en) * 1984-10-01 1986-04-09 Mobay Chemical Corp Glass fiber reinforced polycarbonates
US4722955A (en) * 1985-04-15 1988-02-02 The Dow Chemical Company Thermally stable carbonate polymer composition
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JPH05117382A (ja) * 1991-10-29 1993-05-14 Nippon G Ii Plast Kk 共重合ポリカーボネート、その製造方法およびそれからなる組成物
JPH08319406A (ja) * 1995-05-26 1996-12-03 Kanegafuchi Chem Ind Co Ltd 難燃性樹脂組成物

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See references of WO0029483A1 *

Also Published As

Publication number Publication date
BR9915318A (pt) 2001-08-07
AU1159000A (en) 2000-06-05
JP2002530458A (ja) 2002-09-17
WO2000029483A1 (fr) 2000-05-25
CN1326487A (zh) 2001-12-12
KR20010082298A (ko) 2001-08-29

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