EP1341848A1 - Compositions polycarbonate - Google Patents

Compositions polycarbonate

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Publication number
EP1341848A1
EP1341848A1 EP01991755A EP01991755A EP1341848A1 EP 1341848 A1 EP1341848 A1 EP 1341848A1 EP 01991755 A EP01991755 A EP 01991755A EP 01991755 A EP01991755 A EP 01991755A EP 1341848 A1 EP1341848 A1 EP 1341848A1
Authority
EP
European Patent Office
Prior art keywords
polycarbonate composition
weight
polycarbonate
composition according
parts
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.)
Withdrawn
Application number
EP01991755A
Other languages
German (de)
English (en)
Inventor
Thomas Eckel
Andreas Seidel
Bernd Keller
Dieter Wittmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Original Assignee
Bayer AG
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Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP1341848A1 publication Critical patent/EP1341848A1/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Withdrawn legal-status Critical Current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
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016—Flame-proofing or flame-retarding additives
    • 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
    • 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
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C08L69/005—Polyester-carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • 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
    • 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 invention relates to impact-modified, flame-retardant polycarbonate compositions with improved notched impact strength in the low-temperature range.
  • EP-A 0 640 655 describes molding compositions made from aromatic polycarbonate, styrene-containing copolymers and graft polymers which can be flame-retarded with monomeric and / or oligomeric organic phosphorus compounds.
  • EP-A 0 363 608 discloses flame-retardant polymer mixtures made from aromatic polycarbonate, styrene-containing copolymer or graft copolymer and oligomeric organic phosphates as flame retardant additives.
  • flame-retardant polycarbonate compositions for applications, for example in the vehicle sector, requires a combination of properties of high mechanical strength even in the low-temperature range and excellent flame-resistance. These applications often include safety-relevant parts that can be subjected to high impact or shock loads.
  • the invention is therefore based on the object of impact-modified and at the same time flame-resistant to provide adverse polycarbonate compositions with improved mechanical properties in the low temperature range.
  • compositions which have a special ratio of rubber-containing fraction in the graft polymer to rubber-free fraction of ninyl (co) polymer in the composition.
  • Such compositions preferably have an impact strength of greater than about 20 k / J m 2 , preferably greater than about 25 k / J m 2 , measured according to ISO 180 1A at -20 ° C.
  • the Aii requirements N-0 according to the UL 94 N test are met by the polycarbonate composition according to the invention with a thickness of the test specimen ⁇ 3.2 mm, preferably ⁇ 1.6 mm. This means that a test specimen made from the polycarbonate compositions according to the invention does not exceed 10
  • test specimens do not show a total flame time of more than 50 seconds when exposed twice to each test set; they do not contain any specimens that burn completely up to the holding hammer attached to the upper end of the specimen; they have no samples which ignite the cotton wool arranged below the sample by burning drops or particles.
  • the desired property profile is achieved with polycarbonate compositions which
  • Part B a to the rubber-free part K of vinyl (co) polymer in the polycarbonate composition is greater than 1; is preferably greater than 1.5, particularly preferably greater than 2 and in particular greater than 2.5.
  • the rubber-free portion K is composed of the rubber-free portion
  • the polycarbonate composition according to the invention has a heat resistance according to Vicat B 120 greater than about 100 ° C.
  • compositions according to the invention preferably contain
  • Aromatic polycarbonates and / or aromatic polyester carbonates (component A) which are suitable according to the invention are known or can be prepared by processes known from the literature (for the preparation of aromatic polycarbonates see, for example, Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964 and DE-AS 1 495 626, DE-OS 2 232 877, DE-OS 2 703 376, DE-OS 2 714 544, DE-OS 3 000 610, DE-OS 3 832 396; for the production of aromatic polyester carbonates, for example
  • Aromatic polycarbonates can be prepared by reacting diphenols with carbonic acid halides, preferably phosgene, and / or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalides, by the phase interface method, optionally using chain terminators, for example monophenols and optionally using functional or more than non-functional branching agents , for example triphenols or tetraphenols.
  • Diphenols for the preparation of the aromatic polycarbonates and / or aromatic polyester carbonates are preferably those of the formula (I)
  • B each C 1 -C 4 -alkyl, preferably methyl, halogen, preferably chlorine and / or bromine
  • R ⁇ and R> individually selectable for each oil, independently of one another hydrogen or Cj to Cg-alkyl, preferably hydrogen, methyl or ethyl,
  • n is an integer from 4 to 7, preferably 4 or 5, with the proviso that on at least one atom X, Rß and R ⁇ are simultaneously alkyl.
  • Preferred diphenols are hyclroquinone, resorcinol, dihydroxydiphenols, bis-
  • diphenols are 4,4'-dihydroxydiphenyl, bisphenol-A, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxypheny ⁇ ) 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-hydroxy ⁇ henyl ) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane or 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane. 2,2-bis (4-hydroxyphenyl) propane (bisphenol-A) is particularly preferred.
  • the diphenols can be used individually or as 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-OS 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.- Octylphenol, p-dodecylphenol and 2- (3,5-di- methylheptyl) phenol and 4- (3,5-dimethylheptyl) phenol.
  • 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 by scattered light measurement) from 10,000 to 200,000, preferably 15,000 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 non-functional compounds, for example those with three and more phenolic groups.
  • copolycarbonates Both homopolycarbonates and copolycarbonates are suitable.
  • copolycarbonates according to component A 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, polydiorganosiloxanes with hydroxyaryloxy end groups can also be used. These are known, for example, from US 3,419,634 and can be produced by processes known from the literature. The preparation of copolycarbonates containing polydiorganosiloxane is described in DE-OS 33 34 782.
  • preferred polycarbonates are the copolycarbonates of bisphenol A with up to 15 mol%, based on the molar sum of diphenols, of those other than those mentioned as preferred or particularly preferred
  • Diphenols especially 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane.
  • Aromatic dicarboxylic acid dihalides for the production of aromatic polyester carbonates are preferably the diacid dichlorides of isophthalic acid, terephthalic acid, diphenylemer-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 in the production of polyester carbonates.
  • the 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 d to C 2 -alkyl groups or by halogen atoms, and aliphatic C 2 to C 2 - 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 built-in aromatic hydroxycarboxylic acids. They can be linear or branched in a known manner (DE-OS 2 940 024 and DE-OS 3 007 934).
  • 3- or merirfunctional carboxylic acid chlorides such as trimesic acid trichloride, cyanuric acid trichloride, 3,3 '-, 4,4'-benzophenonetetracarboxylic acid tetrachloride, 1,4,5,8-naphthalenetetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride, in amounts of 0.01 can be used as branching agents up to 1.0 mol% (based on the dicarboxylic acid dichlorides used) or 3- or polyfunctional phenols, such as
  • Phloroglucin 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hepten-2,4,4-dimefhyl-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 (4-hydroxyphenyl) cyclohexyl] propane, 2,4-bis (4-hydroxyphenylisopropyl) phenol, tetra- (4-hydroxyphenyl) methane, 2,6-bis (2-hydroxy-5-methyl-benzyl) ) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane, tetra- (4- [4-hydroxy- phenyl-isopropyl] phenoxy) methane,
  • 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
  • Both the ester and carbonate content of the aromatic polyester carbonates can be in the form of blocks or randomly distributed in the polycondensate.
  • the relative solution viscosity ( ⁇ rel ) of the aromatic polycarbonates and polyester carbonates is in the range from 1.18 to 1.4, preferably from 1.20 to 1.32 (measured on solutions of 0.5 g of polycarbonate or polyester carbonate in 100 ml of methylene chloride solution) 25 ° C).
  • thermoplastic, aromatic polycarbonates and polyester carbonates can be used alone or in any mixture. They can be contained in the composition in an amount of 40 to 99, preferably 60 to 98.5 parts by weight.
  • Component B comprises one or more graft polymers of
  • Bl 5 to 95 preferably 30 to 90 wt .-%, of at least one vinyl monomer B.2 95 to 5, preferably 70 to 10% by weight of one or more graft bases with glass transition temperatures ⁇ 10 ° C, preferably ⁇ 0 ° C, particularly preferably ⁇ -20 ° C.
  • the graft base B.2 generally has an average particle size (dso value) of 0.05 to 10 ⁇ m, preferably 0.1 to 5 ⁇ m, particularly preferably 0.2 to 1 ⁇ m.
  • Monomers B.l are preferably mixtures of
  • vinyl aromatics and / or core-substituted vinyl aromatics such as styrene, ⁇ -methylstyrene, p-methylstyrene, p-chlorostyrene
  • -C-C 8 alkyl esters such as methyl methacrylate, ethyl meth - acrylate
  • B.1.2 1 to 50 parts by weight of vinyl cyanides (unsaturated nitriles such as acrylonitrile and methacrylonitrile) and / or (meth) acrylic acid (C 1 -C 8 ) alkyl esters, such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and / or derivatives (such as anhydrides and lnides) of unsaturated carboxylic acids, for example maleic anhydride and N-phenyl-maleimide.
  • vinyl cyanides unsaturated nitriles such as acrylonitrile and methacrylonitrile
  • acrylic acid (C 1 -C 8 ) alkyl esters such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and / or derivatives (such as anhydrides and lnides) of unsaturated carboxylic acids, for example maleic anhydride and N-phenyl-
  • Preferred monomers B.l.l are selected from at least one of the monomers styrene, ⁇ -methylstyrene and methyl methacrylate
  • preferred monomers B.l.2 are selected from at least one of the monomers acrylonitrile, maleic anhydride and methyl methacrylate.
  • Particularly preferred monomers are B.l.l styrene and B.l.2 acrylonitrile.
  • Graft bases B.2 suitable for the graft polymers B are, for example, diene rubbers, EP (D) M rubbers, that is to say those based on ethylene / propylene and, if appropriate, diene, acrylate, polyurethane, silicone, chloroprene and ethylene / vinyl acetate rubbers.
  • Preferred graft bases B.2 are diene rubbers, for example based on butadiene and isoprene, or mixtures of diene rubbers or copolymers of diene rubbers or their mixtures with other copolymerizable monomers (for example according to B1 and B1), with the proviso that the glass transition temperature of the component B.2 is below ⁇ 10 ° C, preferably ⁇ 0 ° C, particularly preferably ⁇ -10 ° C. Pure polybutadiene rubber is particularly preferred.
  • Particularly preferred polymers B are, for example, ABS polymers (emulsion, bulk and suspension ABS), such as those used e.g. in DE-OS 2 035 390
  • the gel percentage of the. Graft base B.2 is at least 30% by weight, preferably at least 40% by weight (measured in toluene).
  • the graft copolymers B are obtained by radical polymerization, e.g. prepared by emulsion, suspension, solution or bulk polymerization, preferably by emulsion or bulk polymerization.
  • Particularly suitable graft rubbers are also ABS polymers that pass through
  • Redox initiation with an initiator system made of organic hydroperoxide and ascorbic acid according to US Pat. No. 4,937,285.
  • the graft monomers are not necessarily grafted completely onto the graft base in the grafting reaction,
  • Graft polymers B are also understood to mean those products which are obtained by (co) polymerizing the graft monomers in the presence of the graft base and are also obtained in the working up.
  • the rubber-containing fraction B a (expressed in parts by weight) of component B for the
  • the ratio Z is the insoluble component of the graft polymer merisats.
  • the rubber-free portion K results from the copolymer (B ⁇ ) obtained in the graft polymerization, which is soluble, and the copolymer (C), which can additionally be added to the mixture as component C).
  • the rubber-free portion K of the copolymer is the sum of the amount Bj and C (in parts by weight).
  • the ratio Z is B a / K.
  • the rubber-free fraction in the graft polymer is determined by extracting the soluble fraction with the aid of a suitable solvent such as, for example, methylene chloride, acetone, methyl ethyl ketone, dimemylfoimamide, dimethyl acetate or mixtures of 2 or more of these solvents. After generally known workup e.g. Precipitation, you get the soluble portion in the graft polymer. The proportion of the insoluble rubber-containing components can then be calculated from this.
  • a suitable solvent such as, for example, methylene chloride, acetone, methyl ethyl ketone, dimemylfoimamide, dimethyl acetate or mixtures of 2 or more of these solvents.
  • Suitable acrylate rubbers according to B.2 of the polymers B are preferably polymers of acrylic acid alkyl esters, optionally with up to 40% by weight, based on B.2, of other polymerizable, ethylenically unsaturated monomers.
  • the preferred polymerizable acrylic acid esters include Ct to C 8 alkyl esters, for example methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Haloalkyl esters, preferably halogen CrCs alkyl esters, such as chloroethyl acrylate and mixtures of these monomers.
  • Monomers with more than one polymerizable double bond can be copolymerized for crosslinking.
  • Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids with 3 to 8 C atoms and unsaturated monohydric alcohols with 3 to 12 C atoms, or saturated polyols with 2 to 4 OH groups and 2 to 20 C atoms, such as emylene glycol dimethacrylate, allyl - methacrylate; polyunsaturated heterocyclic compounds such as trivinyl and triallyl cyanurate; polyfunctional vinyl compounds such as di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate.
  • Preferred crosslinking monomers are allyl methacrylate, emylene glycol dimethacrylate, diallyl phthalate and hetero- cyclic compounds which have at least three ethylenically unsaturated groups.
  • Particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloylhexahy ⁇ ro-s-friazine and triallylbenzenes.
  • the amount of the crosslinked monomers is preferably 0.02 to 5, in particular 0.05 to 2% by weight, based on the graft base B.2. In the case of cyclic crosslinking monomers with at least three ethylenically unsaturated groups, it is advantageous to limit the amount to less than 1% by weight of the graft base B.2.
  • Preferred "other" polymerizable, ethylenically unsaturated monomers which can be used for preparing the graft base B.2 addition to Acrylklareestern optionally are, for example, acrylonitrile, styrene, ⁇ -methylstyrene, ide Acryla, vinyl-Cr C ö alkyl ethers, methyl methacrylate, .Butadien , Preferred acrylate rubbers as graft base B.2 are emulsion polymers which have a gel content of at least 60% by weight.
  • graft bases according to B.2 are silicone rubbers with graft-active sites, as are described in DE-OS 3 704 657, DE-OS 3 704 655, DE-OS 3 631 540 and DE-OS 3 631 539.
  • the gel content of the graft base B.2 is determined at 25 ° C. in a suitable solvent (M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik I and ⁇ , Georg Thieme-Verlag, Stuttgart 1977).
  • the graft polymers can in the composition according to the invention in one
  • Amount from 0.5 to 60, preferably 1 to 40 and most preferably 2 up to 25 parts by weight can be used. Mixtures of different graft polymers can also be present.
  • Component C comprises one or more thermoplastic vinyl (co) polymers C.l and / or polyalkylene terephthalates C.2.
  • Suitable vinyl (co) polymers C.I. polymers of at least one monomer from the group of the vinyl aromatics, vinyl cyanides (unsaturated nitriles),
  • Cll 50 to 99 preferably 60 to 80 parts by weight of vinyl aromatics and / or nuclear-substituted vinyl aromatics such as styrene, ⁇ -methylstyrene, p-methylstyrene, p-chlorostyrene) and / or methacrylic acid (C 1 -C 8 ) alkyl esters such as methyl methacrylate, ethyl methacrylate), and
  • Nitriles such as acrylonitrile and methaeryl nitrile and / or (meth) acrylic acid (C 1 -C 8 ) alkyl esters, such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and / or unsaturated carboxylic acids, such as maleic acid, and / or derivatives, such as anhydrides and imides, unsaturated carboxylic acids, for example maleic anhydride and N-phenylmaleimide).
  • C 1 -C 8 alkyl esters such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and / or unsaturated carboxylic acids, such as maleic acid, and / or derivatives, such as anhydrides and imides, unsaturated carboxylic acids, for example maleic anhydride and N-phenylmaleimide).
  • the vinyl (co) polymers C.l are resin-like, thermoplastic and rubber-free.
  • the copolymer of C.I. 1 styrene and C.1.2 acrylonitrile is particularly preferred.
  • the (co) polymers according to C.l are known and can be radicalized
  • the (co) polymers preferably have average molecular weights Mw. (Weight average, determined by light scattering or sedimentation) between 15,000 and 200,000.
  • the polyalkylene terephthalates of component C.2 are reaction products of aromatic dicarboxylic acids or their reactive derivatives, such as dimethyl esters or anhydrides, and aliphatic, cycloaliphatic or araliphatic diols and mixtures of these reaction products.
  • Preferred polyalkylene terephthalates contain at least 80% by weight, preferably at least 90% by weight, based on the dicarboxylic acid component of terephthalic acid residues and at least 80% by weight, preferably at least 90 mol%, based on the diol component of ethylene glycol and / or butanediol -l, 4-residues.
  • the preferred polyalkylene terephthalates can contain up to
  • the preferred polyalkylene terephthalates can contain up to 20 mol%, preferably up to 10 mol%, other aliphatic diols with 3 to 12 carbon atoms or cycloaliphatic diols with 6 to 21 Contain carbon atoms, e.g. Residues of propanediol-1,3,2-ethylpropanediol-1,3, neopentylglycol,
  • Pentanediol-1 5, hexanediol-1,6, cyclohexane-dimethanol-1,4,3-ethylpentanediol-2,4,2-methylpentanediol-2,4,2,2,4-trimethylpentanediol-1,2,2 Ethylhexanediol-1, 3, 2,2-diethylpropanediol-1,3, hexanediol-2,5, l, 4-di- (ß-hydroxyethoxy) benzene, 2,2-bis (4-hydroxycyclohexyl) propane, 2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane, 2,2-bis (4-ß-hydroxyethoxy-phenyl) propane and 2,2-bis (4-hydroxypropoxyphenyl) propane
  • the polyalkylene terephthalates can be branched by incorporating relatively small amounts of trihydric or tetravalent alcohols or 3- or 4-basic carboxylic acids, for example according to DE-A 1 900270 and US Pat. No. 3,692,744.
  • preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and propane and
  • polyalkylene terephthalates which have been produced solely from terephthalic acid and its reactive derivatives (e.g. its dialkyl esters) and ethylene glycol and / or 1,4-butanediol, and mixtures of these polyalkylene terephthalates.
  • Polyalkylene terephthalates contain 1 to 50% by weight, preferably 1 to 30% by weight, polyethylene terephthalate and 50 to 99% by weight, preferably 70 to 99% by weight, polybutylene terephthalate.
  • the polyalkylene terephthalates preferably used generally have an intrinsic viscosity of 0.4 to 1.5 dl / g, preferably 0.5 to 1.2 dl / g, measured in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C. in the Ubbelohde viscometer.
  • the polyalkylene terephthalates can be prepared by known methods (see e.g. Kunststoff-Handbuch, Volume Vm, p. 695 ff., Carl-Hanser-Verlag, Kunststoff 1973).
  • the vinyl (co) polymers or polyalkylene terephthalates can be present in the composition according to the invention in amounts of 0 to 45, preferably 1 to 30 and particularly preferably 2 to 25 parts by weight.
  • Phosphorus-containing flame retardants (D) in the sense of the invention are preferably selected from the groups of the mono- and oligomeric phosphorus and phosphonic acid esters, phosphonatamines and phosphazenes, mixtures of several components selected from one or different of these groups also being able to be used as flame retardants.
  • Other halogen-free phosphorus compounds not specifically mentioned here can also be used alone or in any combination with other halogen-free phosphorus compounds.
  • Preferred mono- and oligomeric phosphoric or phosphonic acid esters are phosphorus compounds of the general formula (IN)
  • Rl, R ⁇ , R3 and R ⁇ independently of one another in each case optionally halogenated C 1 -C 6 -alkyl, each optionally substituted by alkyl, preferably C 1 -C 4 -alkyl, and / or halogen, preferably chlorine, bromine, C5-Cg- Cycloalkyl, C to C20-rl or C7 to Ci2-aralkyl,
  • n independently of one another, 0 or 1
  • X is a mono- or polynuclear aromatic radical with 6 to 30 C atoms, or a linear or branched aliphatic radical with 2 to 30 C atoms, which can be OH-substituted and can contain up to 8 ether bonds.
  • R 1 , R 2 , R 3 and R 4 independently of one another are C to C4-alkyl, phenyl, naphthyl or phenyl -CC-C4-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 C to C4 alkyl.
  • Particularly preferred aryl radicals are cresyl, phenyl, xylenyl, propylphenyl or butylphenyl and the corresponding brominated and chlorinated derivatives thereof.
  • X in the formula (IN) preferably denotes a mono- or polynuclear aromatic radical having 6 to 30 carbon atoms. This is preferably derived from diphenols of the formula (I).
  • n in the formula (IN), independently of one another, can be 0 or 1, preferably n is 1.
  • q stands for values from 0 to 30.
  • Components of the formula (IN) can be used in mixtures, preferably number-average q values of 0.3 to 20, particularly preferably 0.5 to 10, in particular 0.5 to 6.
  • X particularly preferably stands for
  • X is derived from resorcinol, hydroquinone, bisphenol A or diphenylphenol.
  • X is particularly preferably derived from bisphenol A.
  • the use of oligomeric phosphoric acid esters of the formula (TV), which are derived from bisphenol A, is particularly advantageous since the compositions equipped with this phosphorus compound have a particularly high resistance to stress cracking and hydrolysis and a particularly low tendency to form deposits in injection molding processing. Furthermore, these flame retardants can achieve a particularly high heat resistance.
  • Monophosphorus compounds of the formula (IN) are, in particular, tributyl phosphate, tris (2-chloroethyl) phosphate, tris (2,3-dibromobroyl) phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl cresyl phosphate, diphenyl octyl phosphate, diphenyl 2-ethyl cresyl isophosphate, tris ) phosphate, halogen-substituted aryl phosphates, dimethyl methylphosphonate, diphenyl methylphosphate,
  • Phenylphosphonic acid diethyl ester triphenylphosphine oxide or tricresylphosphine oxide.
  • the phosphorus compounds according to component C formula (IN) are known (cf., for example, EP-A 363 608, EP-A 640 655) or can be prepared analogously by known methods (for example Ullmann's Encyclopedia of Industrial Chemistry, vol. 18, p . 301 ff. 1979; Houben-Weyl, Methods of Organic Chemistry, Vol. 12/1, p. 43; Beilstein Vol. 6, p. 177).
  • the mean q values can be determined by using a suitable method
  • GC Gas Chromatography
  • HPLC High Pressure Liquid Chromatography
  • GPC Gel Permeation Chromatography
  • Phosphonatamines are preferably compounds of the formula (V) A 3 - - y yN ⁇ Bl y (V)
  • Rl 1 and R 2 independently of one another for unsubstituted or substituted
  • Rl3 and Rl4 independently of one another for unsubstituted or substituted C ⁇ to Cjo-alkyl or unsubstituted or substituted Cß to C ⁇ o ⁇
  • Rl3 and Rl4 together represent unsubstituted or substituted C3 to C ⁇ Q alkylene
  • the numerical values mean 0, 1 or 2 and ßl independently represents hydrogen, optionally halogenated C2 to Cg-alkyl, unsubstituted or substituted Cg to Cio-aryl.
  • ßl preferably independently represents hydrogen, ethyl, n- or iso-propyl, which may be substituted by halogen, unsubstituted or by
  • Alkyl in RÜ, R1 ⁇ 5 R13 and R14 s en independently preferably for methyl, ethyl, n-propyl, iso-propyl, n-, iso-, sec. or tert-butyl, pentyl or hexyl.
  • Substituted alkyl in R 3 and R 4 independently preferably represent halogen-substituted C 1 -C 10 -alkyl, in particular mono- or di-substituted methyl, ethyl, n-propyl, iso-propyl, n-, iso-, sec. or tert-butyl, pentyl or hexyl.
  • Cg to cyryl in R ⁇ , R ⁇ , R ⁇ and R 4 independently preferably represents phenyl, naphthyl or binaphthyl, especially o-phenyl, o-naphthyl, o-binaphthyl, which by halogen (generally one, two - or triple) can be substituted.
  • R13 and R14 together with the oxygen atoms to which they are directly attached and the phosphorus atom can form an Rmg structure.
  • Rl 1, Rl2 5 R13 and R 4 have the meanings given above.
  • Compounds of the formulas (Va-2) and (Va-1) are particularly preferred.
  • the preparation of the phosphonate amines is described, for example, in US Pat. No. 5,844,028.
  • Phosphazenes are compounds of the formulas (Via) and (Nlb)
  • R is in each case identical or different and for amino, in each case optionally halogenated, preferably halogenated with fluorine to Cg-alkyl, or Ci to Cg-alkoxy, in each case optionally with alkyl, preferably Ci to C4-alkyl, and / or halogen, preferably chlorine and / or bromine, substituted
  • C5 to Cö-cycloalkyl C to C20 aryl, preferably phenyl or naphthyl, Cß to C20 aryloxy, preferably phenoxy, naphthyloxy, or C7 to C12 aralkyl, preferably phenyl-C ⁇ -C4-alkyl,
  • Phenoxyphosphazene is preferred.
  • the phosphazenes can be used alone or as a mixture.
  • the radical R can always be the same or 2 or more radicals in the formulas (Ia) and (Ib) can be different.
  • Phosphazenes and their preparation are described for example in EP-A 728 811, DE-A 1 961668 and WO 97/40092.
  • the flame retardants can be used alone or in any mixture with one another or in a mixture with other flame retardants.
  • the phosphorus-containing flame retardant can be used in an amount of 0.1 to 30, preferably 1 to 25 and most preferably 2 to 20 parts by weight in the composition according to the invention.
  • the flame retardants according to component D are often used in combination with so-called anti-dripping agents, which reduce the tendency of the material to burn in the event of a fire.
  • Compounds of the substance classes of fluorinated polyolefins, silicones and aramid fibers may be mentioned here as examples. These can also be used in the compositions according to the invention.
  • Fluorinated polyolefins are preferably used as anti-dripping agents.
  • the fluorinated polyolefins are generally present in the mixture in an amount of 0.01 to 3, preferably 0.05 to 1.5 parts by weight.
  • Fluorinated polyolefins are known and are described, for example, in EP-A 0 640 655. They are sold under the Teflon ® brand, for example Teflon 30N by DuPont.
  • the fluorinated polyolefins can be used both in pure form and in the form of a coagulated mixture of emulsions of the fluorinated polyolefins with emulsions of the graft polymers (component B) or with an emulsion of a copolymer, preferably based on styrene / acrylonitrile, the fluorinated -
  • the polyolefin is mixed as an emulsion with an emulsion of the graft polymer or of the copolymer and then coagulated.
  • the fluorinated polyolefins can be used as a precompound with the graft polymer (component B) or a copolymer, preferably based on styrene / acrylonitrile.
  • the fluorinated polyolefins are mixed as a powder with a powder or granulate of the graft polymer or copolymer and are compounded in the melt generally at temperatures from 200 to 330 ° C. in conventional units such as internal kneaders, extruders or twin-screw screws.
  • the fluorinated polyolefins can also be used in the form of a masterbatch which is prepared by emulsion polymerization of at least one monoethylenically unsaturated monomer in the presence of an aqueous dispersion of the fluorinated polyolefin.
  • Preferred monomer components are styrene, acrylonitrile and mixtures thereof. After acidic precipitation and subsequent drying, the polymer is used as a free-flowing powder.
  • the coagulates, precompounds or masterbatches usually have solids contents of fluorinated polyolefin of 5 to 95% by weight, preferably 7 to 60% by weight.
  • Component F comprises very finely divided inorganic powders, which may only be added in up to an amount, so that the claimed impact strength is retained.
  • Suitable very finely divided inorganic powders F preferably consist of at least one polar compound of one or more metals of the 1st to 5th main group or 1st to 8th subgroup of the periodic table, preferably the 2nd to 5th main group or 4th to 8th subgroup, particularly preferably the 3rd to 5th
  • Main group or 4th to 8th subgroup or from compounds of these metals with at least one element selected from oxygen, hydrogen, sulfur, phosphorus, boron, carbon, nitrogen or silicon.
  • Preferred compounds are, for example, oxides, hydroxides, water-containing
  • the very finely divided inorganic powders preferably consist of oxides, phosphates, hydroxides, preferably of TiO 2 , SiO 2 , SnO 2 , ZnO, ZnS, boehmite, ZrO 2 , Al 2 O 3 ,
  • nanoscale particles can be surface-modified with organic molecules in order to achieve better compatibility with the polymers. In this way, hydrophobic or hydrophilic surfaces can be created.
  • Hydrated aluminum oxides for example boehmite or TiO 2 , are particularly preferred.
  • the average particle diameters of the nanoparticles are less than or equal to 200 ⁇ m, preferably less than or equal to 150 nm, in particular 1 to 100 nm.
  • Particle size and particle diameter always means the mean particle diameter d 50 , determined by ultracentrifuge measurements according to W. Scholtan et al., Kolloid-Z. and Z. Polymers 250 (1972), pp. 782-796.
  • the inorganic powder is incorporated into the thermoplastic molding composition in amounts of 0.5 to 40, preferably 1 to 25, particularly preferably 2 to 15% by weight, based on the thermoplastic material.
  • the inorganic compounds can be present as powders, pastes, brine dispersions or suspensions. Precipitation can be used to obtain powders from dispersions, brine or suspensions.
  • the powders can be incorporated into the thermoplastic molding compositions by customary processes, for example by directly kneading or extruding molding compositions and the very finely divided inorganic powders.
  • Preferred methods are the preparation of a master batch, e.g. in flame retardant additives and at least one component of the molding compositions according to the invention in monomers or solvents, or the co-precipitation of a thermoplastic component and the very finely divided inorganic powders, e.g. by co-precipitation of an aqueous emulsion and the finely divided inorganic powders, optionally in the form of dispersions, suspensions, pastes or sols of the finely divided inorganic materials.
  • the molding compositions according to the invention can contain at least one of the customary additives, such as lubricants and mold release agents, for example pentaethylthritol tetrastearate, nucleating agents, antistatic agents, stabilizers, fillers and reinforcing materials different from component F), and also dyes and pigments.
  • Preferred reinforcing materials are glass fibers.
  • Preferred fillers, which can also have a reinforcing effect, are glass balls, mica, silicates, quartz, talc and titanium dioxide.
  • the molding compositions according to the invention can contain up to 35% by weight, based on the
  • Total molding compound another, optionally synergistic flame retardant contain.
  • Organic halogen compounds such as decabromobisphenyl ether, tetrabromobisphenol, inorganic halogen compounds such as ammonium bromide, nitrogen compounds such as melamine, melamine formaldehyde resins and inorganic hydroxide compounds such as are exemplified as further flame retardants
  • inorganic compounds such as antimony oxides, barium metaborate, hydroxoantimonate, zirconium oxide, zirconium hydroxide, molybdenum oxide, ammonium molybdate, zinc borate, ammonium borate, barium metaborate, talc, silicate, silicon oxide and tin oxide as well as siloxane compounds.
  • the fillers and reinforcing materials and additional flame retardants may only be added to the molding composition according to the invention in such quantities that it does not fall below the required notched impact strength value.
  • compositions according to the invention are prepared by mixing the respective constituents in a known manner and melt-compounding and melt-extruding them at temperatures from 200 ° C. to 300 ° C. in conventional units such as internal kneaders, extruders and twin-screw screws.
  • the individual constituents can be mixed in a known manner both successively and simultaneously, both at about 20 ° C. (room temperature) and at a higher temperature.
  • thermoplastic molding compositions according to the invention are suitable on account of their excellent flame resistance, in particular the short afterburn time, and their good mechanical properties in the low-temperature range and their high heat resistance Dimensional stability for the production of moldings of all kinds, especially those with increased demands on mechanical properties in the low temperature range, such as in the automotive sector. Due to the heat resistance and theological properties, processing temperatures of> 240 ° C are preferred.
  • the molding compositions according to the invention can be used to produce moldings of any kind.
  • moldings can be produced by injection molding.
  • the compositions are also suitable for the following applications: household appliances, monitors, printers, copiers or
  • Cover plates for the construction sector and parts for rail vehicles can also be used in the field of electrical engineering because they have very good electrical properties, interior components for vehicles, ships, buses, other motor vehicles and aircraft, hubcaps, housings for electrical equipment containing small transformers, housings for devices for disseminating information and
  • Another form of processing is the production of molded articles by deep drawing from previously produced sheets or foils.
  • Another object of the present invention is therefore also the use of the molding compositions according to the invention for the production of moldings of any kind, preferably those mentioned above, and the moldings from the molding compositions according to the invention.
  • the rubber-containing fraction B a is determined to be 80% by weight and the rubber-free fraction is determined to be 20% by weight (based on B).
  • Strol / -A-ylnitrile copolymer with a styrene / acrylonitrile weight ratio of 72:28 and an intrinsic viscosity of 0.55 dl / g (measurement in dimethylformamide at 20 ° C).
  • Triphenyl phosphate Disflamoll TP ® from Bayer AG.
  • compositions are mixed on a 3-1 internal kneader.
  • the moldings are produced on an Arburg 270 E injection molding machine at 260 ° C.
  • the notched impact strength ai is determined in accordance with ISO 180/1 A.
  • the heat resistance according to Vicat B is determined in accordance with DIN 53 460 (ISO 306) on rods measuring 80 x 10 x 4 mm 3 .
  • the fire behavior of the samples was determined according to UL Subj. 94 V measured on rods measuring 127 x 12.7 x 1.6 mm, produced on an injection molding machine at 260 ° C.

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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 une composition polycarbonate à résilience modifiée, contenant un polymérisat greffé et des agents ignifuges. Le rapport Z de la part Ba contenant du caoutchouc, comprise dans le polymérisat greffé (B), sur la part K de (co)polymérisat vinylique libre de caoutchouc, est supérieur à 1 dans la composition polycarbonate selon l'invention.
EP01991755A 2000-12-08 2001-11-26 Compositions polycarbonate Withdrawn EP1341848A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10061080 2000-12-08
DE10061080A DE10061080A1 (de) 2000-12-08 2000-12-08 Polycarbonat-Zusammensetzungen
PCT/EP2001/013709 WO2002046305A1 (fr) 2000-12-08 2001-11-26 Compositions polycarbonate

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EP1341848A1 true EP1341848A1 (fr) 2003-09-10

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JP (1) JP2005506388A (fr)
KR (1) KR20040055725A (fr)
CN (1) CN1489617A (fr)
AR (1) AR031644A1 (fr)
AU (1) AU2002231641A1 (fr)
BR (1) BR0115994A (fr)
CA (1) CA2436597A1 (fr)
DE (1) DE10061080A1 (fr)
MX (1) MXPA03004993A (fr)
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US7303810B2 (en) 2001-03-05 2007-12-04 3Form, Inc. Fire-resistant architectural resin materials
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DE10255824A1 (de) * 2002-11-29 2004-06-09 Bayer Ag Schlagzähmodifizierte Blends
US20060046017A1 (en) 2004-09-01 2006-03-02 3Form Architectural glass panels with embedded objects and methods for making the same
DE102006012990A1 (de) * 2006-03-22 2007-09-27 Bayer Materialscience Ag Flammgeschützte schlagzähmodifizierte Polycarbonat-Zusammensetzungen
CN103481611B (zh) * 2007-05-08 2015-12-23 亨特道格拉斯工业瑞士有限责任公司 施加纹理的多元颜色系统
CN101418117B (zh) * 2007-10-26 2013-06-26 帝人化成株式会社 芳香族聚碳酸酯树脂组合物
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CA2718835C (fr) * 2008-03-22 2016-05-24 Bayer Materialscience Ag Compositions de polycarbonate a resilience modifiee presentant une bonne combinaison d'argile brute et de stabilite a l'hydrolyse et a la fusion
DE102009014878A1 (de) 2009-03-25 2010-09-30 Bayer Materialscience Ag Flammgeschützte schlagzähmodifizierte Polycarbonat-Zusammensetzungen
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KR20110077881A (ko) * 2009-12-30 2011-07-07 제일모직주식회사 투명성 및 난연성이 우수한 인계 아크릴계 공중합체 수지 및 그 조성물
DE102010041387A1 (de) 2010-09-24 2012-03-29 Bayer Materialscience Aktiengesellschaft Flammgeschützte schlagzähmodifizierte Batteriegehäuse auf Polycarbonatbasis I
KR20130002789A (ko) 2011-06-29 2013-01-08 제일모직주식회사 컬러필터용 감광성 수지 조성물 및 이를 이용한 컬러필터
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MXPA03004993A (es) 2004-02-12
CN1489617A (zh) 2004-04-14
US20020115761A1 (en) 2002-08-22
WO2002046305A1 (fr) 2002-06-13
KR20040055725A (ko) 2004-06-26
TW584653B (en) 2004-04-21
AU2002231641A1 (en) 2002-06-18
JP2005506388A (ja) 2005-03-03
AR031644A1 (es) 2003-09-24
RU2003120517A (ru) 2004-12-27
DE10061080A1 (de) 2002-06-13
CA2436597A1 (fr) 2002-06-13

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