EP1325080A1 - Compose a base de copolycarbonates - Google Patents

Compose a base de copolycarbonates

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Publication number
EP1325080A1
EP1325080A1 EP01967335A EP01967335A EP1325080A1 EP 1325080 A1 EP1325080 A1 EP 1325080A1 EP 01967335 A EP01967335 A EP 01967335A EP 01967335 A EP01967335 A EP 01967335A EP 1325080 A1 EP1325080 A1 EP 1325080A1
Authority
EP
European Patent Office
Prior art keywords
composition according
formula
copolycarbonate
weight
alkyl
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Withdrawn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
EP01967335A
Other languages
German (de)
English (en)
Inventor
Holger Warth
Thomas Eckel
Dieter Wittmann
Silke Kratschmer
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
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from DE2000147483 external-priority patent/DE10047483A1/de
Priority claimed from DE10105714A external-priority patent/DE10105714A1/de
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP1325080A1 publication Critical patent/EP1325080A1/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Withdrawn legal-status Critical Current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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
    • 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
    • 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
    • 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

Definitions

  • the invention relates to thermoplastic polycarbonate compositions and moldings containing them with increased stress crack resistance and thermal stability.
  • the resistance to stress cracking of molded articles made of polymers is always important in the manufacture and use of the molded articles when there is contact with oils, cleaning agents and alcohols.
  • chemical-resistant molded articles have long been sought, which on the one hand are resistant to low temperatures and on the other hand have high thermal stability.
  • the task was therefore to find a polycarbonate blend which, on the other hand, shows improved stress cracking behavior and increased thermal stability in comparison to polycarbonate blends which contain polycarbonate from pure 2,2-bis (4-hydroxyphenyl) propane as bisphenol but maintains the beneficial properties of polycarbonate blends, such as excellent low-temperature toughness.
  • Bis (4-hydroxyphenyl) propane is described as particularly resistant to chemicals, heat-resistant and flame-retardant (cf. JP-A 5 117 382, EP-A 0 544407, US-A 5,470,938, US-A 5,532,324 and US-A 5,401,826), in comparison to commercially available polycarbonate made from pure bisphenol A, with the same mechanical properties and transparency.
  • these copolycarbonates can advantageously be used in polycarbonate blends while maintaining the particularly good low-temperature properties.
  • JP-A 03 126 756 describes thermoplastic resin compositions with improved heat resistance, impact resistance, oil and water resistance. These resins are composed of aromatic polyester resin, aromatic polycarbonate and butadiene rubber.
  • EP-A 0 403 837 describes thermoplastic polycarbonate molding compositions based on substituted dihydroxydiphenylcycloalkanes, other aromatic ones
  • Polycarbonates for example based on bisphenol-A, and grafted, particulate diene rubbers and their use for the production of thermoplastic molded bodies. Because of the dihydroxydiphenylcycloalkanes, these molding compositions have improved heat resistance while maintaining good Ke b impact strength.
  • the present invention has for its object to provide thermoplastic polycarbonate compositions with improved stress crack resistance and improved thermal stability.
  • thermoplastic aromatic copolycarbonate composed of 0.1 mol% to 46 mol% of compounds of the formula (I)
  • R 1 to R 8 independently of one another are hydrogen, halogen, to C 8 alkyl
  • Ci Ci to C 5 cycloalkyl, C 6 to C 10 aryl and C 7 to C 12 aralkyl and complementary amounts, ie 99.9 mol% to 54 mol% of diphenols other than Neritatien of formula (T),
  • copolycarbonates according to component A) according to the invention preferably contain 11 to 34 mol% and particularly preferably 26 to 34 mol% of Neritatien of formula (I).
  • Diphenols which are different from Neritatien of formula (I) are correspondingly contained in complementary amounts, that is 99.99 to 54 mol%, preferably 89 to 66 mol%, particularly preferably 74 to 66 mol%.
  • R 1 to R 8 in formula (I) independently of one another preferably represent hydrogen, C 1 -C 4 -alkyl, phenyl, substituted phenyl or halogen, particularly preferably hydrogen, methyl or tert-butyl, particularly preferably all represent same rest.
  • Particularly preferred compounds of the formula (I) are 4,4'-dihydroxydiphenyl (DOD) and 4,4 , -dihydroxy-3,3 , -5,5'-tetra- (tert-butyl) diphenyl.
  • Preferred diphenols other than compounds of the formula (I) are diphenols of the formula (II)
  • a C ⁇ -C5-alkylene, C2-C5-alkylidene, Cs-Cö-cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO -, C6-Ci2-aryl en > to the further aromatic optionally rings containing heteroatoms can be condensed,
  • B each C 1 -C 2 alkyl, preferably methyl, halogen, preferably chlorine and / or bromine
  • x each independently of one another 0, 1 or 2
  • p are 1 or 0, and
  • R5 and R6 can be selected individually for each X, independently of one another hydrogen or C -C -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 6 are simultaneously alkyl.
  • Preferred compounds of the formula (IT) are 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -3,3, 5-trimethylcyclohexane and 1,3-bis [2- (4- hydroxyphenyl) -2-propyl] benzene, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, in particular 2,2-bis (4- hydroxyphenyl) propane (bisphenol A).
  • Copolycarbonate as well as several compounds of formula (IT) can be used.
  • the starting materials of the formula (I) and (II) can of course contain impurities due to the synthesis.
  • a high level of purity is desirable and desirable, which is why these educts are used with the highest possible level of purity.
  • the production of polycarbonates with the participation of monomers of the formula (I) is preferably carried out in solution, specifically by the interfacial process and the homogeneous phase process.
  • examples include "Schnell", Chemistry and Physics of Polycarbonates, Polymer Reviews, Nol. 9, interscience Publishers, New York, London, Sydney 1964 and on Polymer Reviews, Volume 10, "Condensation Polymers by Interfacial and Solution Methods", Paul W. Morgan, Interscience Publishers, New York 1965, chap. Vffi, p. 325 and EP
  • Transesterification processes (acetate process and phenyl ester process), for example in US Pat. Nos. 3,494,885, 4,386,186, 4,661,580, 4,680,371, and 4,680,372, in EP-A 26,120, 26,121, 26,684, 28,030, 39,845 , 91 602, 97 970, 79 075, 146 887, 156 103, 234913 and 240 301 and in DE-A 1 495 626 and 2232 977.
  • copolycarbonates according to the invention can contain different end groups. These are introduced by chain breakers. Chain terminators in the sense of the invention are those of the formula (Tfl)
  • R, R and R can independently represent H, optionally branched C1-C34-alkyl / cycloalkyl, C 7 -C 34 -alkaryl or C 6 -C 3 -aryl, for example butylphenol, tritylphenol, cumylphenol, phenol, octylphenol , preferably butylphenol or phenol.
  • the polycarbonates can contain small amounts of 0.02 to 3.6 mol% (based on the Dihydroxy compound) contained on branching.
  • Suitable branching agents are the compounds suitable for polycarbonate production with three or more functional groups, preferably those with three or more than three phenolic OH groups, for example l, l, l-tri- (4-hydroxypheny ⁇ ) ethane and isatin biscresol.
  • thermoplastic, aromatic polycarbonates have average molecular weights (weight average M w , measured for example by an ultracentrifuge or scattered light measurement) of 10,000 to 200,000, preferably 15,000 to 80,000.
  • thermoplastic, aromatic copolycarbonates can be used alone or in any mixture.
  • Another component of the polycarbonate compositions according to the invention is the graft polymer according to component B, which can comprise one or more graft polymers.
  • Monomers B.l are preferably mixtures of
  • vinyl aromatics and / or core-substituted vinyl aromatics such as styrene, methylstyrene, p-methylstyrene, p-chlorostyrene
  • methacrylic acid (C 1 -C 8 ) alkyl esters such as methyl methacrylate , Ethyl methacrylate
  • B12 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 imides of unsaturated carboxylic acids such as 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)
  • derivatives such as anhydrides and imides of unsaturated carboxylic acids such as maleic anhydride and N-phenyl-maleimide.
  • Preferred monomers B.l.l are selected from at least one of the monomers
  • preferred monomers Bl2 selected from at least one of the monomers acrylonitrile, maleic anhydride and methyl methacrylate. Particularly preferred monomers are B1 styrene x B1 B1 acrylonitrile.
  • graft bases B.2 suitable for the graft polymers B are
  • EP (D) M rubbers ie those based on ethylene / propylene and optionally acrylate, polyurethane, silicone, chloroprene and ethylene / vinyl acetate rubbers.
  • Preferred graft bases B.2 are diene rubbers, for example and preferably based on butadiene or isoprene or mixtures of diene rubbers or copolymers of diene rubbers or their mixtures with other copolymerizable monomers, for example according to B1 and B.1.2.
  • Component B.2 preferably has a glass transition temperature of about ⁇ 0 ° C, particularly preferably of ⁇ -20 ° C.
  • the graft base B.2 has an average particle size (d 5 o value) microns in general from 0.05 to 10, preferably from 0.1 microns to 5, particularly preferably 0.2 to 1 micron. Pure polybutadiene rubber is particularly preferred, optionally with up to 30% by weight (based on the rubber base) of comonomer selected from styrene, acrylonitrile, methyl methacrylate or mixtures thereof.
  • Particularly preferred polymers B are e.g. ABS polymers (emulsion, bulk and suspension ABS), as described in DE-A 2 035 390 or in DE-A 2 248 242 or in Ullmanns, Encyclopedia of Industrial Chemistry, Vol. 19 (1980), P. 280 ff. Are described.
  • the gel fraction 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 prepared by radical polymerization, for example by emulsion, suspension, solution or bulk polymerization, preferably by emulsion or bulk polymerization.
  • ABS polymers which are produced by redox initiation with an initiator system of organic hydroperoxide and ascorbic acid according to US Pat. No. 4,937,285 are also particularly suitable graft rubbers.
  • graft polymers B are also understood according to the invention 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.
  • Suitable acrylate rubbers according to B.2 of the polymers B are preferably polymers made from alkyl acrylates, optionally with up to 40% by weight, based on B.2, of other polymerizable, efhylenically unsaturated monomers.
  • the preferred polymerizable acrylic acid esters include C 1 -C 8 -alkyl esters, for example methyl, ethyl, butyl, n-octyl xmd 2-ethylhexyl ester; Haloalkyl esters, preferably halogen (C 1 -C 8) 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 ethylene glycol dimethacrylate, allylneth - acrylate; 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, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds which have at least three ethylenically unsaturated groups.
  • Particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloylhexahydro-s-triazine and triallylbenzenes.
  • the amount of crosslinked monomers is preferably 0.02 to 5, in particular 0.05 to 2,% by weight, based on the graft base B.2.
  • Preferred "other" polymerizable, ethylenically unsaturated monomers which, in addition to the acrylic acid esters can optionally be used to prepare the graft base B.2, are, for example, acrylonitrile, styrene, ⁇ -methylstyrene, acrylamides, vinyl -CC 6 -alkyl ethers, methyl methacrylate, butadiene.
  • Preferred acrylate rubbers as the 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-A 3 704 657, DE-A 3 704 655, DE-A 3 631 540 and DE-A 3 631 539.
  • the gel content of the graft base B.2 is determined at 25 ° C. in a suitable solvent (M. Hoffmann, H. Krämer, R. Kuhn, Polymeranalytik I and II, Georg Thieme-Verlag, Stuttgart 1977).
  • the average particle size d 50 is the diameter above and below which 50% by weight of the particles lie. It can be determined by means of ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. and Z. Polymer 250 (1972), 782-1796).
  • the copolycarbonate composition can contain polymers according to component C as further constituents.
  • Component C comprises one or more thermoplastic vinyl (co) polymers Cl and / or polyalkylene terephthalates C.2.
  • copolycarbonate compositions can be up to 45, preferably up to
  • 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 core-substituted vinyl aromatics such as styrene, ⁇ -methylstyrene, p-methylstyrene, p-chlorostyrene) and / or methacrylic acid (-C-C 8 ) alkyl esters such as Methyl methacrylate, ethyl methacrylate), and
  • vinyl cyanides unsaturated nitriles
  • acrylonitrile and methacrylonitrile xmd / or (meth) acrylic (C 1 -C 8 ) alkyl esters such as methyl methacrylate, n-butyl acrylate, t-Butyl acrylate, xmd / or unsaturated carboxylic acids such as maleic acid and / or derivatives such as anhydrides and imides, more unsaturated
  • Carboxylic acids such as maleic anhydride and N-phenylmaleimide).
  • the (co) polymers Cl are resin-like, thermoplastic and rubber-free.
  • the copolymer of Cl. 1 styrene xmd C.1.2 acrylonitrile is particularly preferred.
  • the (co) polymers according to Cl are known and can be prepared by radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization.
  • the (co) polymers preferably have average molecular weights M w (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 terephthalic acid residues xmd at least 80% by weight, preferably at least 90 mol%, based on the diol component of ethylene glycol and or butanediol 1 , 4-residues.
  • the preferred polyalkylene terephthalates can contain up to 20 mol%, preferably up to 10 mol%, of residues of other aromatic or cycloaliphatic 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%, preferably up to 10 mol%, of other aliphatic ones
  • diols with 3 to 12 carbon atoms or cycloaliphatic diols with 6 to 21 carbon atoms for example residues of 1,3-propanediol, 2-ethylpropanediol, 1,3, neopentylglycol, 1,5-pentanediol, 1,6-hexanediol , Cyclohexane-dimethanol-1,4,3-ethylpentanediol-2,4,2-methylpentanediol-2,4,2,2,4-trimethylpentanediol-1,3,2-ethylhexanediol-1,3,2,2-diethyl propanediol -1,3, hexanediol-2,5,1,4-di- ( ⁇ -hydroxyethoxy) benzene, 2,2-bis- (4-hydroxycyclohexyl) propane, 2,4-dihydroxy-l, 1,3 , 3-te
  • the polyalkylene terephthalates can be prepared by incorporating relatively small amounts of trihydric or tetravalent alcohols or 3- or 4-basic carboxylic acids, e.g. according to DE-A
  • branching agents are Ti ⁇ mesinsäxxre, trimellitic acid, trimethylolethane and -propane and pentaerythritol.
  • 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.
  • Mixtures of polyalkylene terephthalates contain 1 to 50% by weight, preferably
  • 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 an Ubbelohde viscometer.
  • the polyalkylene terephthalates can be prepared by known methods (Kunststoff-Handbuch, Volume VIII, p. 695 ff., Carl-Hanser-Verlag, Kunststoff 1973).
  • the polycarbonate composition according to the invention can contain flame retardants; phosphorus-containing flame retardants are particularly preferred.
  • Phosphorus-containing flame retardants in the sense of the invention are particularly preferably selected from the groups of the mono- and oligomeric phosphorus and phosphonic acid esters, phosphonate amines and phosphazenes, mixtures of several components selected from one or different of these groups can 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 (TV)
  • R ⁇ , RIO, RI I and R 1 ⁇ independently of one another each optionally halogenated Ci to Cg alkyl, in each case optionally substituted by alkyl, preferably C1 -C4 alkyl, and / or halogen, preferably chlorine, bromine, C5 bis Cg-cycloalkyl, C ⁇ to C2 () aryl or C7 to C12 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 9 , R 10 , R 11 and R 12 are preferably independently of one another C 1 -C 4 -alkyl, phenyl, naphthyl or phenyl-C 1 -C 4 -alkyl.
  • aryl radicals are cresyl, phenyl, xylenyl, propylphenyl or butylphenyl and the corresponding brominated and chlorinated derivatives thereof.
  • X in the formula (IV) preferably denotes a mono- or polynuclear aromatic radical having 6 to 30 carbon atoms. This is preferably derived from diphenols of the formula (JJ).
  • n in the formula (TV), 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, a particularly high heat resistance can be achieved with these flame retardants.
  • Monophosphorus compounds of the formula (IN) are, in particular, tributyl phosphate, tris (2-chloroethyl) phosphate, tris (2,3-dibromopropyl) phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl cresyl phosphate, diphenyloctyl phosphate, diphenyl 2-ethylcresyl (isopropyl) phosphate ) -phosphate, halogen-substituted aryl phosphates, dimethyl methylphosphonate, diphenyl methylphosphate,
  • Phenylphosphonic acid diethyl ester triphenylphosphine oxide or tricresylphosphine oxide.
  • the phosphorus compounds of the formula (IN) are known (EP-A 363 608, EP-A 640 655) or can be prepared in an analogous manner by known methods
  • 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 (N) A 3 . y -NBl y (V) in which
  • Rl3 and Rl4 independently of one another represent unsubstituted or substituted C 1 -C IQ-alkyl or unsubstituted or substituted Cö-Ci o-aryl or
  • R ⁇ 3 and Rl4 together represent unsubstituted or substituted C3-Ci Q-alkylene
  • y are the numerical values 0, 1 or 2 and ßl independently represents hydrogen, optionally halogenated C2-Cg-alkyl, unsubstituted or substituted Cg-Ci Q-aryl.
  • ßl preferably independently represents hydrogen, ethyl, n- or iso-propyl, which can be substituted by halogen, unsubstituted or by C1-C4-alkyl and / or halogen-substituted Cö-Ci o-aryl, especially phenyl or naphthyl.
  • Alkyl in R 1 1 , R 1 ⁇ , Rl3 and R 4 independently preferably represents methyl, ethyl, n-propyl, isopropyl, n-, iso-, sec- or tert-butyl, pentyl or hexyl.
  • Substituted alkyl in R Ü , R ⁇ ? R1 and R14 s t s t independently preferably substituted by halogen, C1 -C Q alkyl, in particular mono- or disubstituted methyl, ethyl, n-propyl, iso-propyl, n-, iso-, sec- or tert -butyl.,
  • Cg-Ci Q- aryl in R 11 , R ⁇ , R 1 ⁇ and R * 4 independently preferably represents phenyl, naphthyl or binaphthyl, in particular o-phenyl, o-naphthyl, o-binaphthyl, which by halogen (in general -, Two or three times) can be substituted.
  • R ⁇ 3 and Rl4 can form a ring structure together with the oxygen atoms to which they are directly attached and the phosphorus atom.
  • Rl 1, R 1 ⁇ , R md R 1 ⁇ have the meanings given above.
  • Ner compounds of the formulas (Na-2) and (Na-1) are particularly preferred.
  • Phosphazenes are compounds of the formulas (NIa) and (NTb)
  • R is the same or different and represents amino, in each case optionally halogenated, preferably with fluorine halogenated C ⁇ - to Cg alkyl, or C ⁇ - to Cg alkoxy, each optionally substituted by alkyl, preferably Ci- C4 alkyl, and / or Halogen, preferably chlorine and / or bromine, substituted C5 to Cö-cycloalkyl, Cß to C2 () aryl, preferably phenyl or naphthyl, Cg to C2 () aryloxy, preferably phenoxy, naphthyloxy, or C7 to C ⁇ 2 Aralkyl, preferably phenyl-C4-alkyl, k represents 0 or a number from 1 to 15, preferably a number from 1 to 10.
  • Examples include: propoxyphosphazene, phenoxyphosphazene, methylphenoxyphosphazene, aminophosphazene and fluoroalkylphosphazenes. 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 1 961 668 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 molding compositions according to the invention can at least contain one of the customary additives, such as lubricants and mold release agents, for example pentaerythritol tetrastearate,
  • the filled or reinforced molding compositions can contain up to 60, preferably 10 to 40% by weight, based on the filled or reinforced molding composition, of fillers and / or ner reinforcing materials.
  • Fillers and / or ner reinforcing materials are preferred ner reinforcing materials.
  • Preferred fillers, which can also have a reinforcing effect, are glass balls, mica, silicates, quartz, talc, titanium dioxide, wollastonite.
  • the molding compositions according to the invention can contain up to 35% by weight, based on the
  • flame retardant examples include organic halogen compounds, such as decabromobisphenyl ether, tetrabromobisphenol, inorganic halogen compounds, such as ammonium bromide, nitrogen compounds, such as melamine, melamine formaldehyde resins, inorganic hydroxide compounds, such as Mg, Al hydroxide, inorganic compounds such as antimony oxides, barium metaborate, hydroxoantbutonate, zirconium oxide, zirconium oxide, zirconium oxide, zirconium oxide and zirconium oxide , Arnmonixxmmolybdat, zinc borate, ammonium borate, barium metaborate, talc, silicate, silicon oxide and tin oxide as well as siloxane compounds.
  • organic halogen compounds such as decabromobisphenyl ether, tetrabromobisphenol
  • inorganic halogen compounds such as ammonium bromide, nitrogen compounds, such as melamine, melamine
  • compositions according to the invention are produced by mixing the respective constituents in a known manner and melt-compounding xmd melt-extruding them at temperatures from 200 ° C. to 300 ° C. in conventional units such as internal kneaders, extruders and twin-screw extruders.
  • the individual components 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 afterburning time, and their good mechanical properties and their high heat resistance, for the production of moldings of all kinds, in particular those with increased demands on mechanical properties.
  • the molding compositions can be used to produce moldings of any kind.
  • moldings can be produced by injection molding.
  • Examples of moldings that can be produced are: Housing parts of all types, for example for household appliances such as juicers, coffee machines, mixers, for office machines such as monitors, printers, copiers or cover plates for the construction sector and parts for the automotive Sector. They can also be used in the field of electrical engineering because they have very good electrical properties.
  • the molding compositions according to the invention for the production of interior components for rail vehicles, hubcaps, housings for small transformers containing electrical appliances, housings for devices for disseminating and transmitting information, housings and cladding for medical purposes, massagers and housings therefor, toy vehicles for children, flat wall elements, housings for safety devices, rear spoiler, heat-insulated transport containers, device zxxr for keeping or supplying small animals, molded parts for sanitary and bathing equipment, cover grilles for ventilators, molded parts for garden and tool sheds, housings for garden tools.
  • telecommunication devices such as telephone devices and faxes, computers, printers, scanners, plotters, monitors, keyboards, typewriters, dictation devices, etc.
  • garden tools garden furniture, lawn mower housings, pipes and housings for garden irrigation, garden houses, leaf vacuums, shredders, shredders, sprayers etc.,
  • 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 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 compositions according to the invention.
  • Bisphenol A with an average molecular weight (weight average) of 24970, determined by means of gas permeation chromatography against polystyrene as standard.
  • A5 polycarbonate based on bisphenol A (Makrolon ® 2600, Bayer AG, Leverkusen, Germany).
  • additives stabilizer, mold release agent
  • the polycarbonate compositions according to the invention are produced by compounding the constituents and additives at from 240 ° C. to 300 ° C. in a twin-screw extruder.
  • composition is shown in Table 1.
  • Table 2 shows the results of the investigations with regard to the edge fiber elongation.
  • the samples are exposed in an isooctanol / toluene mixture (1: 1) over a period of 5 minutes to selected marginal fiber stretches.
  • the edge fiber elongation results in 1% edge cracks, otherwise the sample was without cracks. Breakage occurs at an elongation of 1.2%.
  • the samples according to the invention show no negative results. With an edge fiber elongation of 2.4%, cracks also occurred in the samples according to the invention over a period of 68 to 150 minutes.
  • the impact strength according to ISO 180 1A of the samples according to the invention and of the comparison are determined at room temperature and 0 ° C.
  • the results shown in Table 4 show no deterioration compared to the comparison sample within the scope of the measurement accuracy.
  • the numbers 1 and 2 mean no to minimal surface defects or streaking, 4 to 5 mean strong to very strong streaking.

Landscapes

  • 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)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne des composés de copolycarbonate thermoplastiques, et des corps moulés les contenant, ces corps moulés présentant une plus grande résistance au fendillement par contrainte et une thermostabilité plus élevée.
EP01967335A 2000-09-26 2001-09-13 Compose a base de copolycarbonates Withdrawn EP1325080A1 (fr)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
DE10047483 2000-09-26
DE2000147483 DE10047483A1 (de) 2000-09-26 2000-09-26 Verwendung von Copolycarbonaten
DE10059608 2000-12-01
DE10059608 2000-12-01
DE10105714A DE10105714A1 (de) 2000-12-01 2001-02-08 Zusammensetzung auf Basis von Copolycarbonaten
DE10105714 2001-02-08
PCT/EP2001/010560 WO2002026886A1 (fr) 2000-09-26 2001-09-13 Compose a base de copolycarbonates

Publications (1)

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EP1325080A1 true EP1325080A1 (fr) 2003-07-09

Family

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EP01967335A Withdrawn EP1325080A1 (fr) 2000-09-26 2001-09-13 Compose a base de copolycarbonates

Country Status (10)

Country Link
US (1) US6583257B2 (fr)
EP (1) EP1325080A1 (fr)
JP (1) JP2004510025A (fr)
CN (1) CN100537663C (fr)
AU (1) AU2001287732A1 (fr)
BR (1) BR0114145A (fr)
CA (1) CA2423012A1 (fr)
MX (1) MXPA03002581A (fr)
TW (1) TW562836B (fr)
WO (1) WO2002026886A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10135465A1 (de) * 2001-07-20 2003-02-06 Bayer Ag Polycarbonat-Blends
DE10256316A1 (de) * 2002-12-03 2004-06-24 Bayer Ag Polycarbonat-Formmassen
DE10310284A1 (de) * 2003-03-10 2004-09-23 Bayer Materialscience Ag Zusammensetzung auf Basis von Polycarbonaten
JP4746842B2 (ja) * 2004-03-09 2011-08-10 出光興産株式会社 ポリカーボネート樹脂組成物及びその成形品
DE102005040620A1 (de) * 2004-10-11 2006-04-13 Bayer Materialscience Ag Glasfaserverstärkte Polymer-Zusammensetzungen

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DE2329585C2 (de) * 1973-06-09 1984-01-05 Bayer Ag, 5090 Leverkusen Polycarbonat-Formmassen
DE2918883A1 (de) * 1979-05-10 1980-11-20 Bayer Ag Flammwidrige pc-legierungen mit erhoehter spannungsrisskorrosionsbestaendigkeit
DE3430689A1 (de) * 1984-08-21 1986-03-06 Bayer Ag, 5090 Leverkusen Acrylnitrilfreie blende aus polycarbonat, methylmethacrylat, pfropfkautschuk und einem terpolymerisatharz
DE3919043A1 (de) 1989-06-10 1990-12-13 Bayer Ag Polycarbonat-formmassen
JPH03126756A (ja) 1989-10-11 1991-05-29 Nippon Petrochem Co Ltd 熱可塑性樹脂組成物
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Publication number Publication date
WO2002026886A1 (fr) 2002-04-04
US6583257B2 (en) 2003-06-24
CN1476468A (zh) 2004-02-18
AU2001287732A1 (en) 2002-04-08
JP2004510025A (ja) 2004-04-02
BR0114145A (pt) 2003-07-29
US20020123567A1 (en) 2002-09-05
CA2423012A1 (fr) 2003-03-21
TW562836B (en) 2003-11-21
CN100537663C (zh) 2009-09-09
MXPA03002581A (es) 2004-04-20

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