EP2148902A2 - Compositions de polycarbonate à résilience modifiée - Google Patents

Compositions de polycarbonate à résilience modifiée

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Publication number
EP2148902A2
EP2148902A2 EP08758407A EP08758407A EP2148902A2 EP 2148902 A2 EP2148902 A2 EP 2148902A2 EP 08758407 A EP08758407 A EP 08758407A EP 08758407 A EP08758407 A EP 08758407A EP 2148902 A2 EP2148902 A2 EP 2148902A2
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EP
European Patent Office
Prior art keywords
alkyl
weight
component
graft
aryl
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
EP08758407A
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German (de)
English (en)
Inventor
Andreas Seidel
Evgueni Avtomonov
Eckhard Wenz
Thomas Eckel
Herbert Eichenauer
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
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Bayer MaterialScience AG
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Publication of EP2148902A2 publication Critical patent/EP2148902A2/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F253/00—Macromolecular compounds obtained by polymerising monomers on to natural rubbers or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
    • 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
    • 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
    • C08L51/003—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 macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • 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
    • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
    • 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
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds

Definitions

  • the present invention relates to polycarbonate compositions containing special, produced by the process of emulsion polymerization rubbery graft polymers as impact modifier, these compositions are characterized by high hydrolytic stability and high processing stability, and at the same time have good mechanical properties.
  • This invention also relates to the use of the polycarbonate compositions for the production of moldings and the moldings themselves.
  • Polycarbonate compositions containing graft polymers as impact modifiers may vary depending on the purity and additive nature of the toughening modifier, e.g. ABS (acrylonitrile-butadiene-styrene terpolymer), have different stability to hydrolysis and thermal stress.
  • ABS acrylonitrile-butadiene-styrene terpolymer
  • Certain polycarbonate compositions containing emulsion graft polymers as impact modifiers have some technical advantages over polycarbonate compositions containing bulk ABS, e.g. in terms of surface finish (gloss level), so that it is advantageous for some applications to use emulsion graft polymers. If a high hydrolysis stability and thermal stability are required, high demands must be placed on the emulsion graft polymers used, such as, for example, in terms of their purity, the work-up procedure in their preparation and a waiver of certain aids in their preparation.
  • EP-A 0 900 827 discloses impact-modified polycarbonate compositions with improved thermostability comprising emulsion graft polymers, which are described in US Pat Substantially free of components that degrade the polycarbonate.
  • emulsion graft polymers which are described in US Pat Substantially free of components that degrade the polycarbonate.
  • WO-A 99/01489 discloses emulsion graft polymers of the ABS type which are prepared by means of a wide variety of emulsifiers. Among others, sulfosuccinates are mentioned as possible emulsifiers for their preparation.
  • thermoplastic compositions with good weathering stability and scratch resistance can be prepared, the fine and coarse ASA graft polymers and other specific resins, i.a. Maleic anhydride-modified SAN resins.
  • ASA graft polymers for the preparation of the acrylate rubber bases needed for the ASA graft polymers as an elastic, crosslinked core, i.a.
  • special metal salts of sulfosuccinic acid derivatives are used.
  • alkali metal salts of fatty acids or resin acids are used as emulsifiers.
  • DE 697 34 663 T2 describes impact-modified compositions in which a vinyl graft polymer is included as an impact modifier which is prepared by the emulsion polymerization process and preferably in the presence of at least one free-radical polymerizable, i. double bond-containing emulsifier to which, if appropriate, other non-polymerizable emulsifiers can be added, can be produced.
  • the hydrophilic-lipophilic structure of the polymerizable emulsifiers may include all known emulsifier classes, i. nonionic, cationic and anionic emulsifiers.
  • the optionally added non-polymerizable emulsifiers may be any of the usual emulsifiers suitable for emulsion polymerization, i.a. Rosin acid salts (rosinates), fatty acid salts, alkyl sulfate salts, sulfonates, and the like. also Dialkylbernsteinsulfonklaresalze.
  • Polycarbonate compositions with improved impact resistance containing special MBS impact modifiers obtainable by the emulsion polymerization route.
  • MBS impact modifiers for the production of these MBS impact modifiers in the grafting step of Emulsion polymerization for emulsion polymerization conventional emulsifiers, such as fatty acid salts, alkyl sulfates, Alkylnezosulfonate, alkyl phosphates and other dialkylsulfosuccinate salts and common nonionic emulsifiers.
  • thermoplastic compositions which contain styrene-based emulsion polymers.
  • styrene-based emulsion polymers cationic, anionic and nonionic emulsifiers can be used.
  • anionic emulsifiers e.g. Fatty acid salts, alkyl sulfates, alkyl sulfonates, and the like. Sulfosuccinate used.
  • DE 698 27 302 T2 discloses resin compositions with increased impact strength, which can be achieved by adding hollow particulate rubbery graft polymers.
  • the hollow rubber particles are prepared by special processing methods, e.g. produced by swelling with organic solvents, subsequent grafting reaction in emulsion and removal of all volatiles after grafting.
  • emulsifiers e.g. Fatty acid and resin acid metal salts, alkyl and aryl sulfonates, and the like.
  • Sodium dioctyl sulfosuccinate used for the grafting reaction in the preparation of hollow rubbery graft polymers.
  • compositions which comprise ⁇ -methystyrene-acrylonitrile copolymer, polycarbonate and a graft polymer of non-hollow rubber grafting particles with a shell of styrene and acrylonitrile, sodium dioctylsulfosuccinate being used as emulsifier in the grafting step to prepare the graft polymer.
  • the object of the present invention is to provide polycarbonate molding compositions containing at least one emulsion graft polymer as an impact modifier, which are distinguished by a high resistance to hydrolysis and by a high processing stability with simultaneously good mechanical properties.
  • a further object of the invention is to provide flame-retardant polycarbonate molding compositions comprising at least one emulsion graft polymer as an impact modifier, which is distinguished by high resistance to hydrolysis, high processing stability, improved impact strength (ak), improved weld line strength (anF) and at the same time by an improved impact strength Distinguish elongation at break.
  • component B is obtainable by reaction of the component B.l with the graft base B.2 by means of emulsion polymerization, wherein an emulsifier according to formula (I) is used,
  • R 8 are each H, alkyl, cycloalkyl, (aryl) alkyl or alkyl (aryl) having 1 to 30 carbon atoms, preferably methyl, ethyl, propyl, butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, cycloheptyl, (methyl) hexyl, Octyl, (ethyl) hexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, phenyl, benzyl, phenyl substituted with C 1 to C 30 alkyl
  • R 9 is H or a Q to C 30 -alkyl, C 1 to C 30 -aryl, C 1 to C 3 o- (alkyl) aryl, which may in each case also be substituted, preferably H, C 1 to C 30 -alkyl, C 1 to C C 30 - (aryl) alkyl, C 1 to C 30 - (alkyl) aryl, particularly preferably H,
  • Y " is an anionic group, preferably selected from borate (-O-BO (OR 9 ) ' ), boronate
  • z is the number 1 or 2, preferably z is 1,
  • Alkylphosphonium cation more preferably M + Na + or K + , wherein all parts by weight in the present application are normalized such that the sum of the parts by weight of all components A + B + C in the composition 100 give the desired property profile.
  • Aromatic polycarbonates and / or aromatic polyester carbonates according to component A which are suitable according to the invention are known from the literature or can be prepared by processes known from the literature (for example, see Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, 1964, and DE-AS 1 495 626, DE -A 2 232 877, DE-A 2 703 376, DE-A 2 714 544, DE-A 3 000 610, DE-A 3 832 396, for the preparation of aromatic polyester carbonates, eg DE-A 3 077 934) ,
  • Diphenols for the preparation of the aromatic polycarbonates and / or aromatic polyester carbonates are preferably those of the formula (H)
  • A is a single bond, C 1 to C 5 -alkylene, C 2 to C 5 -alkylidene, C 5 to C 6 -cycloalkylidene,
  • Heteroatom-containing rings may be condensed, or a radical of the formula (DT) or (IV)
  • B are each C 1 to C ) 2- alkyl, preferably methyl, halogen, preferably chlorine and / or
  • Each bromine x is independently 0, 1 or 2
  • p is 1 or 0, and
  • R 5 and R 6 are individually selectable for each X 1 independently of one another hydrogen or C to C -
  • Alkyl preferably hydrogen, methyl or ethyl, X 1 carbon and m is an integer from 4 to 7, preferably 4 or 5, with the proviso that at least one atom X 1 , R 5 and R 6 are simultaneously alkyl.
  • Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols, bis- (hydroxyphenyl) - C ⁇ C j -alkanes, bis- (hydroxyphenyl) -C5 -C6 -cycloalkanes, bis- (hydroxyphenyl) ethers, bis- (hydroxyphenyl ) -sulfoxides, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) -sulfones and ⁇ , ⁇ -bis (hydroxyphenyl) -diisopropyl-benzenes and their nuclear-brominated and / or nuclear-chlorinated derivatives.
  • diphenols are 4,4'-dihydroxydiphenyl, bisphenol-A, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) -cyclohexane, 1,1 Bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-dihydroxydiphenylsulfido, 4,4-dihydroxydiphenylsulfone and their di- and tetrabrominated or chlorinated derivatives such as 2,2-bis (3-chloro-4-) hydroxyphenyl) -propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) -propane or 2,2-bis (3,5-dibromo-4-hydroxyphenyl) -propane.
  • 2,2-bis (4-hydroxyphenyl) propane bisphenol-A
  • the diphenols can be used individually or as any mixtures. The diphenols are known from
  • Chain terminators suitable for the preparation 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- [2- (2,4,4 -Trimethylpentyl)] - phenol, 4- (l, 3-tetramethyl-butyl) -phenol according to DE-A 2,842,005 or monoalkylphenols or dialkylphenols with total
  • alkyl substituents such as 3,5-di-tert-butylphenol, p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol and 2- (3,5-dimethylheptyl) 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 particular used
  • thermoplastic, aromatic polycarbonates have weight average molecular weight (M w , measured, for example, by GPC, ultracentrifuge or scattered light measurement) of 10,000 to 200,000 g / mol, preferably 15,000 to 80,000 g / mol, particularly preferably 24,000 to 32,000 g / mol ,
  • thermoplastic, aromatic polycarbonates may be branched in a known manner, preferably by the incorporation of from 0.05 to 2.0 mol%, based on the sum of the diphenols used, of trifunctional or more than trifunctional compounds, for example those containing three and more phenolic groups.
  • both homopolycarbonates and copolycarbonates are suitable.
  • inventive copolycarbonates according to component A it is also possible to use from 1 to 25% by weight, preferably from 2.5 to 25% by weight, based on the total amount of diphenols to be used, of hydroxyaryloxy endblocked polydiorganosiloxanes. These are known (US 3 419 634) and can be prepared by literature methods. The preparation of polydiorganosiloxane-containing copolycarbonates is described in DE-A 3 334 782.
  • Preferred polycarbonates are, in addition to the bisphenol A homopolycarbonates, the copolycarbonates of bisphenol A with up to 15 mol%, based on the molar amounts of diphenols, of other than preferred or particularly preferred diphenols, in particular 2,2-bis (3,5 dibromo-4-hydroxyphenyl) -propane.
  • Aromatic dicarboxylic acid dihalides for the preparation of aromatic polyester carbonates are, preferably, the diacid dichlorides of isophthalic acid, terephthalic acid, diphenyl ether-4,4 1 - dicarboxylic acid and naphthalene-2,6-dicarboxylic acid.
  • a carbonyl halide preferably phosgene, is additionally used as the bifunctional acid derivative.
  • the amount of chain terminators is in each case 0.1 to 10 mol%, based on moles of diphenol in the case of the phenolic chain terminators and on moles of dicarboxylic acid dichloride in the case of monocarboxylic acid chloride chain terminators.
  • the aromatic polyester carbonates may also contain incorporated aromatic hydroxycarboxylic acids.
  • the aromatic polyester carbonates can be branched both linearly and in a known manner (see DE-A 2 940 024 and DE-A 3 007 934).
  • branching agents are trifunctional or polyfunctional carboxylic acid chlorides, such as trimesic acid trichloride, cyanuric trichloride, 3,3 ', 4,4'-benzophenone-tetracarboxylic acid tetrachloride, 1-.S j ⁇ -naphthalene tetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride, in amounts of 0, 01 to 1.0 mol% (based on the dicarboxylic acid dichlorides used) or trifunctional or polyfunctional phenols, such as phloroglucinol, 4 ) 6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hept-2-ene, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tri (4-hydroxyphenyl) benzene, 1,1,1-tri- (4-hydroxyphenyl ) ethane
  • the proportion of carbonate structural units can vary as desired.
  • the proportion of carbonate groups is preferably up to 100 mol%, in particular up to 80 mol%, particularly preferably up to 50 mol%, based on the sum of ester groups and carbonate groups.
  • Both the ester and the carbonate portion of the aromatic polyester carbonates may be present in the form of blocks or randomly distributed in the polycondensate.
  • the relative solution viscosity ( ⁇ re ⁇ ) of the aromatic polycarbonates and polyester carbonates is in the range 1.18 to 1.4, preferably 1.20 to 1.32 (measured on solutions of 0.5 g of polycarbonate or polyester carbonate in 100 ml of methylene chloride solution at 25 ° C).
  • thermoplastic, aromatic polycarbonates and polyester carbonates can be used alone or in any desired mixture.
  • Component B comprises one or more graft polymers of B.1 5 to 95, preferably 30 to 90 wt .-%, of at least one vinyl monomer
  • the graft base B.2 has, in general, an average particle size (d 5 o-value) of 0.05 to 10 microns, preferably 0.1 to 5 microns, more preferably 0.2 to 0.8 microns.
  • Monomers B.l are preferably mixtures of
  • Preferred monomers B.1.1 are selected from at least one of the monomers styrene and methyl methacrylate
  • preferred monomers B.1.2 are selected from at least one of the monomers acrylonitrile, maleic anhydride and methyl methacrylate.
  • Particularly preferred monomers are B.1.1 styrene and B.1.2 acrylonitrile.
  • Suitable graft bases B.2 for the graft polymers B are diene rubbers, EP (D) M rubbers, ie those based on ethylene / propylene and optionally diene, acrylate, polyurethane, silicone, chloroprene and ethylene / vinyl acetate rubbers.
  • Preferred grafting bases B.2 are diene rubbers, for example based on butadiene and isoprene, or mixtures of diene rubbers or copolymers of diene rubbers or mixtures thereof with other copolymerizable monomers (for example according to B.1.1 and B.1.2), with the proviso that the glass transition temperature of Component B.2 below ⁇ 10 0 C, preferably ⁇ 0 0 C, particularly preferably ⁇ -10 0 C.
  • Especially preferred is pure polybutadiene rubber.
  • the gel content of the graft base B.2 is at least 30% by weight, preferably at least
  • the graft base B.2 is prepared by free-radical polymerization, e.g. by emulsion, suspension, solution or bulk polymerization, preferably by emulsion polymerization.
  • grafted polymers B are also those products which are obtained by (co) polymerization of the grafting monomers in the presence of the grafting base and are obtained during workup.
  • Suitable acrylate rubbers according to B.2 of the polymers B are preferably polymers of alkyl acrylates, optionally with up to 40 wt .-%, based on B.2 other polymerizable, ethylenically unsaturated monomers.
  • the preferred polymerisable acrylic acid esters include C 1 to C 6 alkyl esters, for example methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Haloalkyl esters, preferably halo-Ci-Cg-alkyl esters, such as chloroethyl acrylate and mixtures of these monomers.
  • crosslinking monomers having more than one polymerizable double bond can be copolymerized.
  • Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids having 3 to 8 C atoms and unsaturated monohydric alcohols having 3 to 12 C atoms, or saturated polyols having 2 to 4 OH groups and 2 to 20 C atoms, such as ethylene glycol di (meth ) acrylate, trimethylolpropane tri (meth) acrylate, allyl (meth) 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 (meth) acrylate, ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, diallyl phthalate and heterocyclic compounds having at least three ethylenically unsaturated groups.
  • Particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloylhexa-hydro-s-triazine, trivinylbenzenes.
  • the crosslinking monomers can be used individually, but also in mixtures.
  • the amount of crosslinking monomers is preferably 0.02 to 5, in particular 0.05 to 2 wt .-%, based on the graft B.2.
  • For cyclic crosslinking monomers having at least three ethylenically unsaturated groups it is advantageous to limit the amount to less than 1 wt .-% of the graft B.2.
  • Preferred "other" polymerizable, ethylenically unsaturated monomers which may optionally be used in addition to the acrylic acid esters for the preparation of the graft base B.2 are, for example, acrylonitrile, styrene, ⁇ -methylstyrene, (meth) acrylamides, vinyl-C 1 -C 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 40 wt .-% (measured in toluene at 25 0 C).
  • graft bases according to B.2 are silicone rubbers with graft-active sites, as 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 graft base B.2 is determined at 25 0 C in a suitable solvent (M. Hoffmann, H. Kromer, R. Kuhn, polymer analysis I and ⁇ , Georg Thieme-V succumbed, Stuttgart 1977).
  • the average particle size d 5 o is the diameter, above and below which each 50 wt .-% of the particles are. It can be determined by means of ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid.Z. and Z. Polymere 250 (1972), 782-796).
  • the graft base B.2 can be prepared by the emulsion polymerization process. Usually polymerized at
  • Emulsifiers for example alkali metal salts of alkyl or alkylarylsulfonic acids,
  • alkali metal salts in particular the Na and K salts, of alkyl sulfonates, sulfosuccinates, fatty acids or
  • Carboxylic acids with 10 to 30 carbon atoms are Carboxylic acids with 10 to 30 carbon atoms.
  • emulsifier for the preparation of the rubber base in the present invention depends on the criteria known to those skilled in the art, e.g. the latex shear stability and the nature of the latex particles, particle size, particle size distribution, viscosity, residual monomer content, gel content and thus, in contrast to the teaching of EP-A 0 900 827, do not depend on the exclusion of components which decompose the polycarbonate. According to the present invention, e.g.
  • Alkali metal salts of rosin acids alkali metal salts of higher fatty acids having 10 to 30 carbon atoms, alkali metal salts of specific dicarboxylic acids (such as described in DE 3 639 904 A1), alkali metal salts of alkyl or aryl sulfates or sulfosuccinates or alkali metal salts.
  • Emulsifier mixtures and combinations of ionic and nonionic emulsifiers may also be used in the manner known to those skilled in the art.
  • the choice of emulsifier is crucial in the grafting reaction. It has surprisingly been found that not all conventional emulsifiers can be used in the grafting reaction, as described, for example, in WO 99/01489 A1 in US Pat Production of graft polymers for particularly light ABS molding compositions are described. In order to achieve the object according to the invention, only the anionic emulsifiers according to formula (I) are suitable in the grafting reaction.
  • an anionic emulsifier of the formula (V) is used in the grafting reaction
  • R 9 and Y ' have the abovementioned meaning
  • EWG independently of one another have the meaning explained above
  • F represents an alkylidene group -CR 10 R 1 ' -, wherein
  • R 10 and R 11 are each independently H, alkyl, cycloalkyl, (aryl) alkyl,
  • Alkyl aryl, alkoxy or aryloxy group having 1 to 30 carbon atoms, preferably H, methyl, ethyl, propyl, butyl, pentyl, cyclopentyl, hexyl, cyclohexyl,
  • an anionic emulsifier of the formula (VI) is used in the grafting reaction
  • R 12 and R 13 are each independently H, alkyl, cycloalkyl, (aryl) alkyl or alkyl (aryl) of I to 30 carbon atoms, preferably methyl, ethyl, propyl, butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, cycloheptyl, (Methyl) hexyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, phenyl, benzyl, with Ci to C 3 o-alkyl-substituted phenyl (such as methyl, ethyl , Propyl, butyl, pent
  • Tridecyl phenyl
  • C 2 to Qoo ethoxylated fatty alcohol radicals having 1 to 130 carbon atoms C 3 to C 99 propoxylated fatty alcohol radicals having 4 to 129 carbon atoms, C 2 to C 100 ethoxylated (alkyl) phenol radicals having 3 to 130 carbon atoms, C 3 to C 9 9 propoxylated (alkyl) phenol radicals having 4 to 129 carbon atoms, particularly preferably propyl, butyl, pentyl, cyclopentyl, hexyl,
  • M + is selected from the group of alkali metals (such as Li + , Na + , K + , Rb + , Cs + ), preferably Na + or K + .
  • emulsifiers are known and commercially available, such as Aerosol OT ®, ® TR aerosol, aerosol Al ® 96 (Aerosol types from. Cytec Industries Inc.), Empimin OT ®, Empimin ® OP (Empimin grades from. Hunstman), Geropon ® CYA 75, Geropon ® SDS, Geropon ® SS O 75, Geropon ® WS 25 I (Geropon grades from. Rhodia), Triton ® GR (Fa. Dow Chemical), Lutensit ® A BO ( Fa. BASF).
  • emulsifiers can be used both individually, but also as mixtures with one another, as well as in combination with other non-ionic emulsifiers known to the skilled person for the purpose of better stabilization of the dispersion.
  • sulfosuccinic acid dicyclohexyl diester is used as the emulsifier in the grafting reaction.
  • the emulsifiers for the graft reaction in the preparation of the component B of the compositions according to the invention are in the amounts of 0.1 to 5 wt.%, Preferably from 0.1 to 3 wt.%, Particularly preferably from 0.1 to 1.5 wt .% Based on the monomers used in the preparation of the graft polymer used.
  • the amount of water used to prepare the graft polymer dispersion is preferably such that the finished dispersion has a solids content of from 20 to 50% by weight.
  • radical formers which decompose at the chosen reaction temperature, ie both those which thermally decompose alone, as well as those which do so in the presence of a redox system.
  • it is peroxides, preferred
  • Peroxosulfates such as sodium or potassium peroxodisulfate.
  • redox systems in particular those based on hydroperoxides such as cumene hydroperoxide or tertiary
  • the polymerization initiators in an amount of 0.05 to 1 wt .-%, based on the grafting monomers (B.1) used.
  • radical formers and also the emulsifiers and, if appropriate, the molecular weight regulators explained in the next paragraph are added in portions to the reaction mixture, for example batchwise as total amount at the beginning of the reaction or divided into several portions
  • the continuous addition can also be done along a
  • molecular weight regulators such. As ethylhexyl thioglycolate, n- or t-dodecyl mercaptan and / or other mercaptans, terpinols and / or dimeric ⁇ -methyl styrene and / or other suitable compounds for controlling the molecular weight, concomitantly used.
  • the molecular weight regulators are added to the reaction mixture batchwise or continuously, as described above for the free-radical formers and emulsifiers.
  • molecular weight regulators are used in the polymerization, they can be added in the preparation of the graft base B.2 or in the preparation of the graft B.l or both in the preparation of graft B.2 and graft B.l in the manner described above.
  • the workup of the dispersion of the emulsion Pfrop ⁇ olymerisats B takes place in a method known in the art, without any special requirements on the purity of the reclaimed graft polymer are made: the graft polymer B is, for example, initially precipitated from the dispersion, for example by adding precipitating acting
  • Saline solutions such as calcium chloride, magnesium sulfate, alum
  • acids such as acetic acid
  • Hydrochloric acid or sulfuric acid or else by freezing (freeze coagulation) or precipitation by means of high shear forces (so-called shear precipitation), the high shear forces being generated, for example, by rotor / stator systems or by forcing the dispersion through a narrow gap.
  • shear precipitation high shear forces
  • the resulting aqueous phase is separated in a conventional manner, for example by sieving, filtering, decanting or centrifuging.
  • the water-moist graft polymer is obtained, which usually has a residual water content of up to 60 wt .-%.
  • excipients e.g. Emulsifiers, salts, buffering agents, so that a substantial portion of up to 100% of the excipients (i.e., emulsifiers and other adjuvants) remain in the graft polymer and thus in the final product.
  • excipients e.g. Emulsifiers, salts, buffering agents
  • spray-drying may be used in which the dispersion, without first being coagulated, is converted into fine droplets distributed in the air or inert gas and subsequently dried to powder in air or inert gas countercurrent. All excipients then remain 100% in the final product.
  • Component C comprises one or more thermoplastic vinyl (co) polymers C1 and / or polyalkylene terephthalates C.2.
  • Vmyl (co) polymers Cl polymers of at least one monomer the group of vinyl aromatics, vinyl cyanides (unsaturated nitriles), (meth) acrylic acid (C] -Cg) - alkyl esters, unsaturated carboxylic acids and derivatives (such as anhydrides and imides) of unsaturated carboxylic acids.
  • Particularly suitable are (co) polymers of
  • 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 Cl are resinous, thermoplastic and rubber-free. Particularly preferred is the copolymer of C.1.1 styrene and Cl .2 acrylonitrile.
  • the (co) polymers according to Cl are known and can be prepared by free-radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization.
  • the (co) polymers preferably have average molecular weights Mw (weight average, determined by light scattering or sedimentation) of 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 wt .-%, preferably at least 90 wt .-%, based on the dicarboxylic acid terephthalate and at least 80 wt .-%, preferably at least 90 mol%, based on the diol component of ethylene glycol and / or butanediol-1 , 4-residues.
  • the preferred polyalkylene terephthalates may contain up to 20 mol%, preferably up to 10 mol%, of other aromatic or cycloaliphatic dicarboxylic acids having 8 to 14 carbon atoms or aliphatic dicarboxylic acids having 4 to 12 carbon atoms, such as radicals of Phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid.
  • other aromatic or cycloaliphatic dicarboxylic acids having 8 to 14 carbon atoms or aliphatic dicarboxylic acids having 4 to 12 carbon atoms such as radicals of Phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, a
  • the preferred polyalkylene terephthalates may contain up to 20 mol%, preferably up to 10 mol%, of other aliphatic diols having 3 to 12 carbon atoms or cycloaliphatic diols having 6 to 21 carbon atoms.
  • radicals for example radicals of propanediol 1, 3, 2-ethylpropanediol 1, 3, neopentyl glycol, pentanediol 1, 5, hexanediol-1,6, cyclohexane-dimethanol-1,4, 3-ethylpentanediol-2, 4, 2-methylpentanediol-2,4, 2,2,4-trimethylpentanediol-1,3, 2-ethylhexanediol-1,3,3,2-diethylpropanediol-1,3-hexanediol-2,5,1,4 Di ( ⁇ -hydroxyethoxy) benzene, 2,2-bis (4-hydroxycyclohexyl) propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis (4 - ⁇ -hydroxyethoxy-phenyl) -propane and 2,2-bis (4-hydroxypropoxyphenyl
  • the polyalkylene terephthalates can be prepared by incorporation of relatively small amounts of trihydric or trihydric alcohols or 3- or 4-basic carboxylic acids, e.g. according to DE-A 1 900 270 and US-PS
  • branching agents are trimesic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol.
  • polyalkylene terephthalates prepared from terephthalic acid alone and their reactive derivatives (e.g., their dialkyl esters) and ethylene glycol and / or butane-1,4-diol, and mixtures of these polyalkylene terephthalates.
  • Mixtures of polyalkylene terephthalates contain from 1 to 50% by weight, preferably from 1 to 30% by weight, of polyethylene terephthalate and from 50 to 99% by weight, preferably from 70 to 99% by weight, of polybutylene terephthalate.
  • the preferably used polyalkylene terephthalates generally have a limiting 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, for example, Kunststoff-Handbuch, Volume VHI, page 695 ff, Carl Hanser Verlag, Kunststoff 1973).
  • Phosphorus-containing flame retardants (D) in the sense of the invention are preferably selected from the groups of mono- and oligomeric phosphoric and phosphonic acid esters, phosphonateamines and phosphazenes, whereby mixtures of several components selected from one or more of these groups can be used as flame retardants. Others too Non-specifically mentioned halogen-free phosphorus compounds can 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 (VII)
  • X is a mononuclear or polynuclear aromatic radical having 6 to 30 C atoms or a linear or branched aliphatic radical having 2 to 30 C atoms, which may be OH-substituted and may contain up to 8 ether bonds.
  • R *, R ⁇ , R ⁇ and R 4 are preferably independently C ⁇ to C4 alkyl, phenyl, naphthyl or phenyl-C j -C alkyl.
  • the aromatic groups R 1 , R 1, R 3 and R 4 may in turn be substituted by halogen and / or alkyl groups, preferably chlorine, bromine and / or C ] to C 4 -alkyl.
  • Particularly preferred aryl radicals are cresyl, phenyl, xylenyl, propylphenyl or butylphenyl and the corresponding brominated and chlorinated derivatives thereof.
  • X in the formula (VII) is preferably a mononuclear or polynuclear aromatic radical having 6 to 30 carbon atoms. This is preferably derived from diphenols of the formula (II); n in the formula (VII) may independently be 0 or 1, preferably n is i; q is from 0 to 30, preferably from 0.3 to 20, particularly preferably from 0.5 to 10, in particular from 0.5 to 6, very particularly preferably from 1.0 to 1.6; X is particularly preferred for
  • X is derived from resorcinol, hydroquinone, bisphenol A or diphenylphenol; X is particularly preferably derived from bisphenol A.
  • component D it is also possible to use mixtures of different phosphates.
  • Phosphorus compounds of the formula (VII) are, in particular, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl cresyl phosphate, diphenyl octyl phosphate, diphenyl 2-ethyl cresyl phosphate, tri (isopropylphenyl) phosphate, resorcinol bridged diphosphate and bisphenol A bridged diphosphate.
  • the use of oligomeric phosphoric acid esters of the formula (VII) derived from bisphenol A is particularly preferred.
  • the phosphorus compounds according to component D are known (cf., for example, EP-A 0 363 608, EP-A 0 640 655) or can be prepared by known methods in an analogous manner (eg Ullmanns Enzyklopadie der ischen Chemie, Vol 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 determining the composition of the phosphate mixture (molecular weight distribution) using a suitable method (gas chromatography (GC), high pressure liquid chromatography (HPLC), gel permeation chromatography (GPC)) and from this the mean values for q are calculated.
  • a suitable method gas chromatography (GC), high pressure liquid chromatography (HPLC), gel permeation chromatography (GPC)
  • phosphonatamines and phosphazenes as described in WO 00/00541 and WO 01/18105, can be used as flame retardants.
  • the flame retardants can be used alone or in any mixture with each other or in mixture with other flame retardants.
  • Component E is
  • composition may contain further commercially available additives such as flame retardant synergists, rubber-modified graft polymers other than component B, antidripping agents (for example compounds of the substance classes of the fluorinated polyolefins, of the silicones as well
  • Aramid fibers Aramid fibers
  • lubricants and mold release agents for example pentaerythritol tetrastearate
  • nucleating agents for example pentaerythritol tetrastearate
  • stabilizers antistatic agents (for example carbon blacks, carbon fibers, carbon nanotubes and also organic antistatics such as polyalkylene ethers, alkyl sulfonates or polyamide-containing polymers),
  • Acids, fillers and reinforcing materials for example glass or carbon fibers, mica, kaolin, talc, CaCO 3 and glass flakes
  • dyes and pigments for example, dyes and pigments.
  • the acids according to component E are preferably selected from at least one of the group of the aliphatic dicarboxylic acids, the aromatic dicarboxylic acids and the hydroxy-functionalized dicarboxylic acids. Particular preference is given to citric acid, oxalic acid, terephthalic acid or mixtures of the compounds mentioned.
  • the graft polymers other than component B are prepared by free-radical polymerization, e.g. by emulsion, suspension, solution or bulk polymerization, wherein, in the case of emulsion polymerization, an emulsifier other than formula (I) is used. Preference is given to component B different graft polymers which are prepared by solution or bulk polymerization.
  • thermoplastic molding compositions of the invention are prepared by mixing the particular constituents in a known manner and poundiert schmelzcom- in conventional units such as internal kneaders, extruders and twin-screw at temperatures of 200 0 C to 300 0 C and melt.
  • the mixing of the individual constituents may take place in known manner, either successively or simultaneously, and either at about 2O 0 C (room temperature) or at a higher temperature.
  • the invention also provides processes for the preparation of the molding compositions and the use of the molding compositions for the production of moldings and the moldings themselves.
  • the molding compositions of the invention can be used for the production of moldings of any kind. These can be produced by injection molding, extrusion and blow molding. Another form of processing is the production of moldings by deep drawing from previously prepared plates or films.
  • moldings are films, profiles, housing parts of any kind, e.g. for household appliances such as televisions, juicers, coffee machines, blenders; for office machines such as monitors, flat screens, notebooks, printers, copiers; Panels, pipes, electrical installation ducts, windows, doors and other profiles for the building sector (interior and exterior applications) and electrical and electronic parts such as switches, plugs and sockets, as well as body and interior components for commercial vehicles, in particular for the automotive sector.
  • household appliances such as televisions, juicers, coffee machines, blenders
  • office machines such as monitors, flat screens, notebooks, printers, copiers
  • Panels, pipes, electrical installation ducts, windows, doors and other profiles for the building sector (interior and exterior applications) and electrical and electronic parts such as switches, plugs and sockets, as well as body and interior components for commercial vehicles, in particular for the automotive sector.
  • the molding compositions according to the invention can also be used, for example, for the production of the following moldings or moldings: interior fittings for rail vehicles, ships, aircraft, buses and other motor vehicles, housings of electrical appliances containing small transformers, housings for information processing and transmission equipment, housings and panels for medical applications Apparatus, massagers and housings therefor, toy vehicles for children, flat wall elements, housing for safety devices and for televisions, heat-insulated transport containers, fittings for plumbing and bathroom equipment, grille for ventilation openings and housings for garden tools.
  • A.l linear polycarbonate based on bisphenol A with a weight average
  • A.2 Linear polycarbonate based on bisphenol A having a weight-average molecular weight M w of 28500 g / mol (determined by GPC in CH 2 Cl 2 at 25 ° C.).
  • Component B Type B emulsion graft polymers with polybutadiene rubber base
  • the particulate crosslinked rubber base used for the preparation of component B was prepared by free-radical emulsion polymerization of butadiene in the presence of sodium salt of a specific TCD emulsifier as described in DE 3913509A1 (Example 1).
  • 0-2 parts by weight of each used emulsifier are heated to 65 0 C under nitrogen.
  • 0.4 part by weight of tert-butyl hydroperoxide dissolved in 20 parts by weight of water
  • 0.5 part by weight of sodium ascorbate dissolved in 20 parts by weight of water
  • a mixture of 30 parts by weight of styrene and 10 parts by weight of acrylonitrile is added within 4 hours, wherein the grafting reaction takes place.
  • the latex is coagulated in a magnesium sulfate / acetic acid solution, filtered, optionally washed (see below) and the resulting powder dried at 70 ° C. in vacuo.
  • Emulsifier 1.5 parts by weight of the sodium salt of sulfosuccinic dicyclohexyl diester (Aerosol Al 96, from Cytec Industries).
  • Coagulant work-up the coagulum obtained after the precipitation is filtered off only (about 20 L filtrate solution) and not washed.
  • Graft polymer B (I-Ib): Preparation according to general procedure (I) Emulsifier: 1.5 parts by weight of the sodium salt of sulfosuccinic acid dicyclohexyl diester Coagulation work-up: the coagulum obtained after the precipitation is filtered off and washed once with a large amount of distilled water ( ie about 20 L per 1 kg of polymer).
  • Graft Polymer B (I, Ic): Preparation according to general procedure (I) Emulsifier: 1.5 parts by weight of the sodium salt of sulfosuccinic acid dicyclohexyl diester Coagulate work-up: the coagulum obtained after the precipitation is filtered off and carefully (ie 4 times in distilled water) Slurried water, then filtered off and washed with a large amount of distilled water (a total of about 80 liters per 1 kg of polymer)).
  • Graft polymer B (I-Id): Preparation according to general instructions (I) Emulsifier: 0.5 part by weight of the sodium salt of sulfosuccinic acid dicyclohexyl diester Coagulant work-up: The coagulum obtained after the precipitation is filtered off and not washed.
  • Coagulant work-up the coagulum obtained after the precipitation is filtered off and carefully slurried (i.e., slurried 4 times in distilled water, then filtered off and washed with a large amount of distilled water (a total of about 80 liters per 1 kg of polymer).
  • Graft Polymer B (1.2a) (Comparison): Preparation According to General Procedure (I) Emulsifier: 0.5 part by Weight Sodium Dodecyl Sulfate (Aldrich)
  • Coagulant work-up the coagulum obtained after the precipitation is filtered off and carefully slurried (i.e., slurried 4 times in distilled water, then filtered off and washed with a large amount of distilled water (a total of about 80 liters per 1 kg of polymer).
  • Graft polymer B (1.2b) (comparative): Preparation according to general procedure (I) Emulsifier: 1.0 part by weight Sodium dodecyl sulfate (Aldrich) Coagulant work-up: The coagulum obtained after the precipitation is filtered off and carefully (ie 4 times in distilled water) Slurried water, then filtered off and washed with a large amount of distilled water (a total of about 80 liters per 1 kg of polymer)).
  • Graft Polymer B (1.2c) (Comparison): Preparation According to General Procedure (I) Emulsifier: 1.5 parts by weight of sodium dodecylsulfate (Aldrich)
  • Coagulant work-up the coagulum obtained after the precipitation is filtered off and carefully slurried (i.e., slurried 4 times in distilled water, then filtered off and washed with a large amount of distilled water (a total of about 80 liters per 1 kg of polymer).
  • Emulsifier 2 parts by weight of the sodium salt of sulfosuccinic acid dicyclohexyl diester (aerosol
  • Coagulant work-up the coagulum obtained after the precipitation is filtered off only (about 20 L filtrate solution) and not washed.
  • Graft polymer B (2.1b): Preparation according to the general procedure (ET) Emulsifier: 2 parts by weight of the sodium salt of sulfosuccinic acid dicyclohexyl diester Coagulate work-up: the coagulum obtained after the precipitation is filtered off and washed once with a large amount of distilled water (ie approx. 20 liters per 1 kg of polymer).
  • E general procedure
  • Emulsifier 2 parts by weight of the sodium salt of sulfosuccinic acid dicyclohexyl diester
  • Coagulate work-up the coagulum obtained after the precipitation is filtered off and washed once with a large amount of distilled water (ie approx. 20 liters per 1 kg of polymer).
  • Graft polymer B (2.1c): Preparation according to general procedure (E) Emulsifier: 2 parts by weight of the sodium salt of sulfosuccinic acid dicyclohexyl diester Coagulate work-up: the coagulum obtained after the precipitation is filtered off and carefully (ie slurried 4 times in distilled water, then filtered off and washed with a large amount of distilled water (a total of about 80 liters per 1 kg of polymer)).
  • Graft polymer B (2.1d): Preparation according to general procedure (II) Emulsifier: 1.5 parts of the sodium salt of sulfosuccinic acid dicyclohexyl diester (Aerosol Al 96) Coagulant work-up: the coagulum obtained after the precipitation is filtered off only (about 20 l filtrate solution) and not washed.
  • Graft Polymer B (2.1e): Preparation According to General Procedure (D) Emulsifier: 1.0 part of the sodium salt of sulfosuccinic acid dicyclohexyl diester (Aerosol Al 96)
  • Coagulant work-up the coagulum obtained after the precipitation is filtered off only (about 20 L filtrate solution) and not washed.
  • Graft polymer B (2.1f): Preparation according to the general procedure (H) Emulsifier: 0.5 part of the sodium salt of sulfosuccinic acid dicyclohexyl diester (Aerosol Al 96)
  • Coagulant work-up the coagulum obtained after the precipitation is filtered off only (about 20 L filtrate solution) and not washed.
  • Graft Polymer B (2.2a) (Comparison): Preparation according to General Method (II) Emulsifier: 2 parts sodium dodecyl sulfate (Aldrich)
  • Coagulant work-up the coagulum obtained after the precipitation is filtered off only (about 20 L filtrate solution) and not washed.
  • Graft Polymer B (2.2b) (Comparison): Preparation according to General Method (II) Emulsifier: 2 parts sodium dodecyl sulfate (Aldrich)
  • Coagulant processing the coagulum obtained after the precipitation is filtered off and washed once with a large amount of distilled water (about 20 L per 1 kg of polymer).
  • Graft Polymer B (2.2c) (Comparison): Preparation according to general instructions (JT) Emulsifier: 2 parts sodium dodecyl sulfate (Aldrich) Coagulant workup: the coagulum obtained after the precipitation is filtered off and carefully (ie, slurried 4 times in distilled water, then filtered off and washed with a large amount of distilled water (in total about 80 liters per 1 kg of polymer)).
  • Emulsifier 0.5 part sodium dodecyl sulfate (Aldrich)
  • Coagulum workup the coagulum obtained after the precipitation is filtered off and carefully (i.e.
  • Emulsifier 1.0 TIe sodium dodecyl sulfate (Aldrich)
  • Coagulum workup the coagulum obtained after the precipitation is filtered off and carefully (i.e.
  • a seed latex was first prepared by polymerizing 10% by weight of n-butyl acrylate in the presence of 83 parts by weight of deionized water, 0.2 part by weight Sodium dodecyl sulfate and 0.18 parts by weight potassium peroxodisulfate (K 2 SaOg) dissolved in 7.0 parts by weight of water for 3 h at 80 0 C.
  • K 2 SaOg potassium peroxodisulfate
  • graft polymers For the preparation of the graft polymers, 180 parts by weight of poly (n-butyl acrylate) latex (solids content 34%) were mixed with 17 parts by weight of water, 0.06 parts by weight of respective emulsifier, dissolved in 1.14 wt . -It water, placed in a flask and heated to 65 0 C under nitrogen. 0.4 part by weight of tert-butyl hydroperoxide, 0.54 part by weight of emulsifier (both components dissolved in 20 parts by weight of water), and 0.5 part by weight of sodium ascorbate (dissolved in 20 parts by weight of water) are added within 7 hours.
  • a mixture of 30 parts by weight of styrene and 10 parts by weight of acrylonitrile is added within 4 hours, wherein the grafting reaction takes place. After a reaction time of 2 hours, a conversion of 99% is achieved.
  • the latex is coagulated with a magnesium sulfate solution, filtered and dried at 70 0 C in a vacuum.
  • Emulsifier 1.5% by weight of the sodium salt of sulfosuccinic acid dicyclohexyl diester
  • Work-up of the graft polymer dispersion The polymer dispersion was precipitated with magnesium sulfate and the coagulum obtained after the precipitation was filtered off (about 2 ⁇ filtrate) and not washed.
  • the processing stability degradation of the polycarbonate at stringent processing conditions
  • the determination of the notched impact strength a ⁇ is carried out in accordance with ISO 180/1 A.
  • the impact resistance at the weld line of specimens injection molded on both sides and measuring 80 mm ⁇ 10 mm ⁇ 4 mm was measured in accordance with ISO 179/1 U.
  • the elongation at break is determined in the tensile test according to ISO 527.
  • compositions 1 to 3 and 8 to 10 show a slight increase in the MVR value after climate storage of 37-50% (DMVR (hydr., Corr.)), Regardless of whether the graft polymer was thoroughly washed or not washed at all
  • compositions of Comparative Examples 5 to 7 and 13 to 15, which contain an ABS prepared with sodium dodecyl sulfate, ie, an emulsifier described in the prior art show that at best DMVR (hydr. corr.) values of 56 to 85% after climate storage can be achieved if the graft polymer has been thoroughly washed, ie no emulsifier is left.
  • DMVR hydro. corr.
  • compositions according to the invention 1 to 3 and 8 to 10 show a good processing stability, which from DMVR (proc.) - values of 37-69% visible (melt storage at 300 0 C, 15 min).
  • compositions 17 to 21 according to the invention from Table 5 show only a moderate increase in the MVR value of 64 to 92% compared to the comparison from the prior art (composition 16) and furthermore have advantages in the notched impact strength (a 1, Bindenahtfestmaschine (a ⁇ ) and the elongation at break.
  • compositions of Table 8 show an analogous behavior: the compositions of the invention have both a good resistance to hydrolysis and a good processing stability, provided that no alpha-methylstyrene-containing polymer is used as component C (cf state of the art DE 698 27 302 T2).
  • component C cf state of the art DE 698 27 302 T2
  • the processing stability relative to composition 26 according to the invention is markedly reduced.

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Abstract

L'invention concerne des compositions de polycarbonate contenant A) 10 - 99 parts en poids de polycarbonate aromatique et/ou de polyestercarbonate aromatique; B) 1 - 35 parts en poids de polymérisat greffé à modification caoutchouc de B.1 5 - 95 parts en poids d'au moins un vinylmonomère sur B.2 95 - 5 parts en poids d'une ou plusieurs bases de greffage ayant une température de transition vitreuse < 10 °C; C) 0 - 40 parts en poids de vinyl(co)polymérisat et/ou de polyalkylène-téréphtalate, avec exclusion d'un copolymérisat d'a-méthylstyrol et d'acrylnitrile, D) 0 à 50 parts en poids par rapport à la somme des constituants A+B+C, d'agent ignifugeant contenant du phosphore; et E) 0 - 50 parts en poids par rapport à la somme des constituants A+B+C, d'agents additifs. Les compositions sont caractérisées en ce que le constituant B peut être obtenu par réaction des constituants B.1 avec la base de greffage B.2 par polymérisation en émulsion au moyen d'un émulsifiant représenté par la formule (I), les compositions étant par ailleurs caractérisées par une grande résistance à l'hydrolyse. L'invention concerne également l'utilisation des compositions de polycarbonate pour la fabrication de corps moulés et les corps moulés eux-même.
EP08758407A 2007-05-16 2008-05-08 Compositions de polycarbonate à résilience modifiée Withdrawn EP2148902A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102007023097 2007-05-16
DE102008015124A DE102008015124A1 (de) 2007-05-16 2008-03-20 Schlagzähmodifizierte Polycarbonat-Zusammensetzungen
PCT/EP2008/003680 WO2008138534A2 (fr) 2007-05-16 2008-05-08 Compositions de polycarbonate à résilience modifiée

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EP2148902A2 true EP2148902A2 (fr) 2010-02-03

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EP (1) EP2148902A2 (fr)
JP (1) JP2010526922A (fr)
KR (1) KR20100016530A (fr)
CN (1) CN101679736A (fr)
BR (1) BRPI0811878A2 (fr)
CA (1) CA2687362A1 (fr)
DE (1) DE102008015124A1 (fr)
MX (1) MX2009011440A (fr)
RU (1) RU2009146338A (fr)
WO (1) WO2008138534A2 (fr)

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KR101599084B1 (ko) * 2008-03-22 2016-03-14 바이엘 머티리얼사이언스 아게 본래 색조, 가수분해 안정성 및 용융 안정성의 우수한 조합을 갖는 내충격성 개질된 폴리카보네이트 조성물
EP2657259A1 (fr) * 2012-04-23 2013-10-30 Bayer MaterialScience AG Compositions d'ABS à surface améliorée après stockage humide à chaud
CN107868430A (zh) * 2017-12-08 2018-04-03 福建麦凯智造婴童文化股份有限公司 一种应用于儿童玩具的工程塑料及其制备方法
CN113563710B (zh) * 2021-09-22 2021-12-21 北京能之光科技有限公司 具有降低内应力的聚碳酸酯的制备方法
CN115678237B (zh) * 2022-10-21 2024-07-12 金发科技股份有限公司 一种缓燃聚碳酸酯复合材料及其制备方法和应用

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RU2009146338A (ru) 2011-06-27
CN101679736A (zh) 2010-03-24
WO2008138534A3 (fr) 2009-05-07
JP2010526922A (ja) 2010-08-05
CA2687362A1 (fr) 2008-11-20
MX2009011440A (es) 2009-11-10
BRPI0811878A2 (pt) 2014-11-18
KR20100016530A (ko) 2010-02-12
DE102008015124A1 (de) 2008-11-20
WO2008138534A2 (fr) 2008-11-20

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