DE102008015124A1 - Impact modified polycarbonate compositions - Google Patents

Abstract

The present invention relates to compositions comprising A) 10-99 parts by weight of aromatic polycarbonate and / or aromatic polyester carbonate, B) 1-35 parts by weight of rubber-modified graft polymer of B.1 5 to 95 of at least one vinyl monomer to B.2 95 C) 0-40 parts by weight of vinyl (co) polymer and / or polyalkylene terephthalate, a copolymer of alpha-methystyrene and acrylonitrile being excluded, D) 0- to 5 of one or more graft bases having a glass transition temperature <10 ° C, 50 parts by weight, based on the sum of the components A + B + C, phosphorus-containing flame retardant, E) 0-50 parts by weight, based on the sum of the components A + B + C, additives, characterized in that component B is obtainable by reaction of the component B.1 with the graft B.2 by means of emulsion polymerization, wherein an emulsifier according to formula (I) is used, wherein these compositions are characterized by a high hydrolysis resistance , and the use of the polycarbonate compositions for the production of moldings and the moldings themselves.

Description

The The present invention relates to polycarbonate compositions containing special, produced by the process of emulsion polymerization rubber-containing graft polymers as impact modifier, these compositions are characterized by a high resistance to hydrolysis and characterized by high processing stability, and at the same time have good mechanical properties. These The invention also relates to the use of the polycarbonate compositions for the production of moldings and the moldings even.

Polycarbonate compositions containing graft polymers as impact modifiers may, depending on the purity and additives of the toughener, z. B. ABS (acrylonitrile-butadiene-styrene terpolymer), have different stability to hydrolysis and thermal stress. So be of BS Patty, L. Novak and H. Phan (in "Thermal and hydrolytic stability of polycarbonates / acrylonitrile-butadiene-styrene based blends", Society of Automotive Engineers, [Special Publication] SP (2005), SP-1960 (Advances in Plastic Components, Processes and Technologies), 145-151) Polycarbonate compositions described that have a much better hydrolytic stability and thermal stability for bulk ABS as a modifier than in the case of emulsion ABS as a modifier. The different behavior of the polycarbonate / bulk ABS compositions compared to polycarbonate / emulsion ABS compositions is attributed to the fact that the production process for emulsion ABS compared to bulk ABS requires a higher number of different chemicals as auxiliaries, such. As emulsifiers, flow improvers, stabilizers, salts, etc., which among these chemicals include those that can lead to the decomposition of the polycarbonate.

Certain Polycarbonate compositions containing emulsion graft polymers as impact modifier have some technical advantages versus polycarbonate compositions containing bulk ABS on, z. B. in terms of surface texture (gloss level), so that it is advantageous for some applications, emulsion graft polymers use. Is a high hydrolytic stability and thermal Stability required, so you have high demands provide the emulsion graft polymers used, such as. B. in terms of their purity, the refurbishment process in their Production and a waiver of certain aids in their Production.

For example, are off EP-A 0 900 827 Impact modified polycarbonate compositions having improved thermostability comprising emulsion graft polymers which are substantially free of components which degrade the polycarbonate. In order to obtain an emulsion graft polymer substantially free of components which degrade the polycarbonate, it is necessary to completely dispense with such components in the emulsion process in each process stage or to free the prepared emulsion graft polymers by a corresponding work-up procedure from these components, for. B. by washing after coagulation of the graft emulsion.

From the WO-A 99/01489 are emulsion-graft polymers of the ABS type known, which are prepared by means of various emulsifiers. Among others, sulfosuccinates are mentioned as possible emulsifiers for their preparation.

The Patent Application US 2006/0106163 teaches that certain thermoplastic Compositions with good weathering stability and scratch resistance can be prepared, the fine and coarse-particle ASA graft polymers and other special resins, u. a. Maleic anhydride-modified SAN resins, included. For the preparation of acrylate rubber bases, those for the ASA graft as elastic, crosslinked Core may be needed, u. a. in addition to common long chain sulphate and sulphonate based metal salts as well special metal salts of sulfosuccinic acid derivatives be used. For the execution of the grafting step for the preparation of ASA emulsion polymers are alkali metal salts of Grease or resin acids used as emulsifiers.

In DE 697 34 663 T2 describes impact-modified compositions in which a Vinylpfropfpolymerisat is contained as impact modifier, which can be produced via the process of emulsion polymerization and preferably in the presence of at least one polymerizable via free-radical polymerization, ie double bond-containing emulsifier to which further non-polymerizable emulsifiers can be added. The hydrophillipophilic structure of the polymerizable emulsifiers may include all known emulsifier classes, ie nonionic, cationic and anionic emulsifiers. The optionally added, non-polymerizable emulsifiers may be all customary for emulsion polymerization emulsifiers, including rosin acid salts (rosinates), fatty acid salts, alkyl sulfate salts, sulfonates and also dialkylsulfuric acid salts.

In the patent EP-A 0390 081 are impact modified polyester and polycarbonate compositions having improved impact resistance which contain specific MBS impact modifiers obtainable by the emulsion polymerization route. For the preparation of these MBS impact modifiers are in the grafting step of the emulsion for emulsion emulsion customary emulsifiers, such as fatty acid salts, alkyl sulfates, Alkylnezosulfonate, alkyl phosphates and other dialkylsulfosuccinate salts and common nonionic emulsifiers.

In JP-A 08067789 describes odorless and thermally stable thermoplastic compositions containing styrene-based emulsion polymers. For the preparation of these styrene-based emulsion polymers cationic, anionic and nonionic emulsifiers can be used. As anionic emulsifiers z. As fatty acid salts, alkyl sulfates, alkyl sulfonates and sulfosuccinates among others.

The DE 698 27 302 T2 discloses resin compositions having increased impact resistance, which can be achieved by adding hollow particulate rubbery graft polymers. The hollow rubber particles are prepared by special process methods, eg. B. by swelling with organic solvents, subsequent grafting reaction in emulsion and removal of all volatiles after grafting. For the grafting reaction in the preparation of hollow rubbery graft polymers known emulsifiers, such as. As fatty acid and resin acid metal salts, alkyl and arylsulfonates, including sodium dioctylsulfosuccinate used. As comparative examples, compositions are disclosed which comprise α-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.

task The present invention is the provision of polycarbonate molding compositions containing at least one emulsion graft polymer as an impact modifier, which is characterized by a high resistance to hydrolysis and characterized by high processing stability at at the same time good mechanical properties.

A Another object of the invention is the provision of flame-retardant Polycarbonate molding compositions containing at least one emulsion graft polymer as an impact modifier, which is characterized by a high hydrolysis resistance, a high processing stability, an improved notched impact strength (ak), Improved Bindenahtfestigkeit (anF) and simultaneously characterized by an improved elongation at break.

• A) 10-99 Gew.-Teile, bevorzugt 40-95 Gew.-Teile, besonders bevorzugt 50-73 Gew.-Teile aromatisches Polycarbonat und/oder aromatisches Polyestercarbonat,
• B) 1-35 Gew.-Teile, bevorzugt 4-30 Gew.-Teile, besonders bevorzugt 12-20 Gew.-Teile kautschukmodifiziertes Pfropfpolymerisat von
• B.1 5 bis 95, vorzugsweise 30 bis 90 Gew.-%, wenigstens eines Vinylmonomeren auf
• B.2 95 bis 5, vorzugsweise 70 bis 10 Gew.-% einer oder mehrerer Pfropfgrundlagen mit einer Glasübergangstemperatur < 10°C, vorzugsweise < 0°C, besonders bevorzugt < -20°C,
• C) 0-40 Gew.-Teile, bevorzugt 1-30 Gew.-Teile, besonders bevorzugt 15-25 Gew.-Teile Vinyl(Co)Polymerisat und/oder Polyalkylenterephthalat, wobei ein Copolymerisat aus α-Methystyrol und Acrylnitril-ausgenommen ist,
• D) 0-50 Gew.-Teile, bevorzugt 1-40 Gew.-Teile, besonders bevorzugt 2-30 Gew.-Teile, jeweils bezogen auf die Summe der Komponenten A + B + C, phosphorhaltiges Flammschutzmittel,
• E) 0-50 Gew.-Teile, bevorzugt 0,5-25 Gew.-Teile, jeweils bezogen auf die Summe der Komponenten A + B + C, Zusatzstoffe,

dadurch gekennzeichnet, dass Komponente B erhältlich ist durch Reaktion der Komponente B.1 mit der Pfropfgrundlage B.2 mittels Emulsionspolymerisation, wobei ein Emulgator gemäß Formel (I) eingesetzt wird,

wobei
EWG eine elektronenziehende Gruppe ist, wie z. B. eine Carbonyl-, eine Carboxyl-, eine Nitril-, eine Nitro- oder eine Sulfongruppe, bevorzugt eine Nitril-, Carbonylgruppe -C(=O)R⁸ oder Carboxylgruppe -CO₂R⁸, besonders bevorzugt eine Carboxylgruppe -CO₂R⁸, wobei
R⁸ jeweils H, Alkyl, Cycloalkyl, (Aryl)alkyl oder Alkyl(aryl) mit 1 bis 30 Kohlenstoffatomen, vorzugsweise 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, mit C₁ bis C₃₀-Alkyl substituiertes Phenyl (wie z. B. Methyl-, Ethyl, Propyl, Butyl-, Pentyl-, Hexyl-, Heptyl-, Octyl-, Nonyl-, Decyl-, Undecyl-, Dodecyl-, (Tridecyl)phenyl) oder jeweils C₂ bis C₁₀₀ ethoxylierte Fettalkoholreste mit 3 bis 130 Kohlenstoffatomen, C₃ bis C₉₉ propoxylierte Fettalkoholreste mit 4 bis 129 Kohlenstoffatomen, C₂ bis C₁₀₀ ethoxylierte (Alkyl)phenolreste mit 3 bis 130 Kohlenstoffatomen, C₃ bis C₉₉ propoxylierte (Alkyl)phenolreste mit 4 bis 129 Kohlenstoffatomen, besonders bevorzugt Propyl, Butyl, Pentyl, Cyclopentyl, Hexyl, Cyclohexyl, Heptyl, Octyl, Nonyl, Decyl, Undecyl, Dodecyl, Tridecyl, insbesondere bevorzugt Hexyl, Cyclohexyl, Heptyl, n-Octyl und 2-Ethylhexyl bedeutet,
W eine Gruppe ist ausgewählt aus C₁- bis C₃₀-Alkyl, C₁- bis C₃₀-Cycloalkyl, C₆- bis C₃₀-Aryl, C₁- bis C₃₀-(Aryl)alkyl, C₁- bis C₃₀-(Alkyl)aryl, C₁- bis C₃₀-Alkoxy, C_l- bis C₃₀-Aryloxy, C₂ bis C₁₀₀ ethoxylierte Alkoxy- oder Aryloxy-Gruppe gemäß der Formel RO-(CH₂-CH₂-O)_a mit a = 1 bis 50 und R = C₁- bis C₃₀-Alkyl oder C₁- bis C₃₀-Aryl, wobei alle genannten Gruppen auch substituiert sein können, z. B. durch eine oder mehrere elektronenziehende Gruppen gemäß obiger Definition für EWG,
R⁹ H oder ein C₁ bis C₃₀-Alkyl, C₁ bis C₃₀-Aryl, C₁ bis C₃₀-(Alkyl)aryl bedeutet, der jeweils auch substituiert sein kann, bevorzugt H, C₁ bis C₃₀-Alkyl, C₁ bis C₃₀-(Aryl)alkyl, C₁ bis C₃₀-(Alkyl)aryl, besonders bevorzugt H bedeutet,
Y^- eine anionische Gruppe ist, bevorzugt ausgewählt aus Borat- (-O-BO(OR⁹)^-), Boronat- (-BO(OR⁹)^-), Nitrat (-O-NO₂ ^-), Nitro- (-NO₂ ^-), Sulfat- (-O-SO₃ ^-), Sulfonat- (-SO₃ ^-), Phosphat- (-O-P(OR⁹)O₂ ^-), Phosphonat- (-P(OR⁹)O₂ ^-), besonders bevorzugt ausgewählt aus Sulfat oder Sulfonat, insbesondere bevorzugt eine Sulfonat-Gruppe -SO₃-, wobei jeweils R⁹ die vorstehend erläuterte Bedeutung hat,
z für die Zahl 1 oder 2 steht, bevorzugt ist z gleich 1,
M^z+ ausgewählt ist für z = 1 aus der Gruppe bestehend aus Alkali-Metallen (wie z. B. Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺), Ammoniumkation, Alkylammoniumkation (NH_4-nR⁹ _n ⁺, wobei n = 1 bis 4 sein kann), Phosphoniumkation und Alkylphosphoniumkation (PH_4-nR⁹ _n ⁺, wobei n = 1 bis 4 sein kann), wobei jeweils R⁹ die vorstehend erläuterte Bedeutung hat, oder für z = 2 ausgewählt ist aus der Reihe der Erdalkalimetalle (wie z. B. Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺), bevorzugt steht M^z+ für M⁺ (d. h. z = 1) und ist ausgewählt aus der Gruppe bestehend aus Li⁺, Na⁺, K⁺, Ammoniumkation, Alkylammoniumkation), Phosphoniumkation und Alkylphosphoniumkation, besonders bevorzugt ist M⁺ Na⁺ oder K⁺,
wobei alle Gewichtsteilangaben in der vorliegenden Anmeldung so normiert sind, dass die Summe der Gewichtsteile aller Komponenten A + B + C in der Zusammensetzung 100 ergeben, das gewünschte Eigenschaftsprofil aufweisen.It has surprisingly been found that compositions containing

• A) 10-99 parts by weight, preferably 40-95 parts by weight, particularly preferably 50-73 parts by weight of aromatic polycarbonate and / or aromatic polyester carbonate,
• B) 1-35 parts by weight, preferably 4-30 parts by weight, more preferably 12-20 parts by weight of rubber-modified graft polymer of
• B.1 5 to 95, preferably 30 to 90 wt .-%, of at least one vinyl monomer on
• B.2 95 to 5, preferably 70 to 10 wt .-% of one or more graft bases having a glass transition temperature <10 ° C, preferably <0 ° C, particularly preferably <-20 ° C,
• C) 0-40 parts by weight, preferably 1-30 parts by weight, more preferably 15-25 parts by weight of vinyl (co) polymer and / or polyalkylene terephthalate, wherein a copolymer of α-methystyrene and acrylonitrile-excepted .
• D) 0-50 parts by weight, preferably 1-40 parts by weight, more preferably 2-30 parts by weight, in each case based on the sum of the components A + B + C, phosphorus-containing flame retardant,
• E) 0-50 parts by weight, preferably 0.5-25 parts by weight, in each case based on the sum of the components A + B + C, additives,

characterized in that component B is obtainable by reaction of component B.1 with the graft base B.2 by means of emulsion polymerization, wherein an emulsifier according to formula (I) is used,

in which
EWG is an electron-withdrawing group, such as Example, a carbonyl, a carboxyl, a nitrile, a nitro or a sulfone group, preferably a nitrile, carbonyl group -C (= O) R ⁸ or carboxyl group -CO ₂ R ⁸ , particularly preferably a carboxyl group -CO ₂ R ⁸ , where
R ^{8 is in} each case 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, C ₁ to C ₃₀ alkyl substituted phenyl (such as methyl -, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, (tridecyl) phenyl) or in each case C ₂ to C ₁₀₀ ethoxylated fatty alcohol radicals having 3 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 ₉₉ propoxylated (alkyl) phenol radicals having 4 to 129 carbon atoms, particularly preferred Propyl, butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, esp especially preferred is hexyl, cyclohexyl, heptyl, n-octyl and 2-ethylhexyl,
W is a group selected from C ₁ to C ₃₀ alkyl, C ₁ to C ₃₀ cycloalkyl, C ₆ to C ₃₀ aryl, C ₁ to C ₃₀ aryl, C ₁ to C ₃₀ - (alkyl) aryl, C ₁ - to C ₃₀ alkoxy, C _l - to C ₃₀ -aryloxy, C ₂ to C ₁₀₀ ethoxylated alkoxy or aryloxy group according to the formula RO- (CH ₂ -CH ₂ -O ) _a with a = 1 to 50 and R = C ₁ - to C ₃₀ -alkyl or C ₁ - to C ₃₀ -aryl, all of which groups may also be substituted, for. By one or more electron-withdrawing groups as defined above for the EEC,
R ^{9 is} H or a C ₁ to C ₃₀ alkyl, C ₁ to C ₃₀ aryl, C ₁ to C ₃₀ - (alkyl) aryl, which may also be substituted in each case, preferably H, C ₁ to C ₃₀ alkyl , C ₁ to 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 (-BO (OR ⁹ ) ^- ), nitrate (-O-NO ₂ ^- ), nitro (- NO ₂ ^- ), sulphate (-O-SO ₃ ^- ), sulphonate (-SO ₃ ^- ), phosphate (-OP (OR ⁹ ) O ₂ ^- ), phosphonate (-P (OR ⁹ ) O ₂ ^- ), particularly preferably selected from sulphate or sulphonate, particularly preferably a sulphonate group -SO ₃ -, where in each case R ^{9 has} the meaning explained above,
z is the number 1 or 2, preferably z is 1,
M ^{z + is} selected for z = 1 from the group consisting of alkali metals (such as Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ ), ammonium cation, alkylammonium cation (NH _4-n R ⁹ _n ⁺ where n = 1 to 4), phosphonium cation and alkylphosphonium cation (PH _4-n R ⁹ _n ⁺ , where n = 1 to 4), wherein each R ^{9 has} the meaning explained above, or selected for z = 2 is from the series of alkaline earth metals (such as Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ ), preferably M ^{z + is} M ⁺ (ie z = 1) and is selected from the group consisting of Li ⁺ , Na ⁺ , K ⁺ , ammonium cation, alkylammonium cation), phosphonium cation and 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.

Surprised it was found that in the preparation of the graft polymer B requires no special purification by means of emulsion polymerization is, for. B. by washing the coagulated graft polymer with up to 100 times the amount of water, as surprisingly despite the whereabouts of the emulsifier in the resulting graft polymer the resulting impact-modified polycarbonate compositions have a high hydrolysis resistance.

Component A

According to the invention, suitable aromatic polycarbonates and / or aromatic polyester carbonates according to component A are known from the literature or can be prepared by processes known from the literature (for the preparation of aromatic polycarbonates, see, for example, Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964 as well as the 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, for. B. DE-A 3 077 934 ).

The Preparation of aromatic polycarbonates z. B. by implementation of diphenols with carbonic acid halides, preferably Phosgene and / or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalides, according to Phase interface method, optionally using chain terminators, for example monophenols and optionally using trifunctional or more than trifunctional Branching, for example, triphenols or tetraphenols. As well is a preparation via a melt polymerization process by reaction of diphenols with, for example, diphenyl carbonate possible.

wobei
A eine Einfachbindung, C₁ bis C₅-Alkylen, C₂ bis C₅-Alkyliden, C₅ bis C₆-Cycloalkyliden, -O-, -SO-, -CO-, -S-, -SO₂-, C₆ bis C₁₂-Arylen, an das weitere aromatische gegebenenfalls Heteroatome enthaltende Ringe kondensiert sein können,
oder ein Rest der Formel (III) oder (IV)

B jeweils C₁ bis C₁₂-Alkyl, vorzugsweise Methyl, Halogen, vorzugsweise Chlor und/oder Brom
x jeweils unabhängig voneinander 0, 1 oder 2,
p 1 oder 0 sind, und
R⁵ und R⁶ für jedes X¹ individuell wählbar, unabhängig voneinander Wasserstoff oder C₁ bis C₆-Alkyl, vorzugsweise Wasserstoff, Methyl oder Ethyl,
X¹ Kohlenstoff und
m eine ganze Zahl von 4 bis 7, bevorzugt 4 oder 5 bedeuten, mit der Maßgabe, dass an mindestens einem Atom X¹, R⁵ und R⁶ gleichzeitig Alkyl sind.Diphenols for the preparation of the aromatic polycarbonates and / or aromatic polyester carbonates are preferably those of the formula (II)

in which
A is a single bond, C ₁ to C ₅ alkylene, C ₂ to C ₅ alkylidene, C ₅ to C ₆ cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO ₂ -, C ₆ to C ₁₂ arylene, to which further aromatic rings containing optionally heteroatoms may be condensed,
or a radical of the formula (III) or (IV)

B is in each case C ₁ to C ₁₂ -alkyl, preferably methyl, halogen, preferably chlorine and / or bromine
x each 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 ₁ to C ₆ -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 on at least one atom X ¹ , R ⁵ and R ^{6 are} simultaneously alkyl.

Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols, bis (hydroxyphenyl) -C ₁ -C ₅ -alkanes, bis (hydroxyphenyl) -C ₅ -C ₆ -cycloalkanes, bis (hydroxyphenyl) ethers, bis (hydroxyphenyl) sulfoxides, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones and α, α-bis (hydroxyphenyl) diisopropyl-benzenes and their nuclear-brominated and / or nuclear-chlorinated derivatives.

Especially preferred 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'-dihydroxydiphenylsulfide, 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. Especially preferred is 2,2-bis- (4-hydroxyphenyl) -propane (bisphenol-A).

The diphenols can be used individually or as any mixtures. The diphenols are known from the literature or available by literature methods.

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- (1,3-tetramethylbutyl) phenol according to DE-A 2 842 005 or monoalkylphenols or dialkylphenols having a total of 8 to 20 carbon atoms in the alkyl substituents, such as 3,5-di-tert-butylphenol, p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol and 2- (3,5- 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 diphenols used in each case.

The thermoplastic aromatic polycarbonates have weight average molecular weights (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.

The thermoplastic, aromatic polycarbonates can be used in branched be known, preferably by the Incorporation of 0.05 to 2.0 mol%, based on the sum of the used Diphenols, on trifunctional or more than trifunctional Compounds, for example those with three and more phenolic Groups.

Both homopolycarbonates and copolycarbonates are suitable. For the preparation of 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 produced by literature methods. The preparation of polydiorganosiloxane-containing copolycarbonates is described in U.S. Patent Nos. 4,378,399 and 5,605,842 DE-A 3 334 782 described.

preferred Polycarbonates are in addition to the bisphenol A homopolycarbonates the Copolycarbonates of bisphenol A with up to 15 mol%, based on the molar sums of diphenols, other than preferred or especially Preferred diphenols, in particular 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane.

aromatic Dicarboxylic acid dihalides for the preparation of aromatic Polyestercarbonates are preferably the diacid dichlorides of isophthalic acid, terephthalic acid, diphenyl ether-4,4'-dicarboxylic acid and naphthalene-2,6-dicarboxylic acid.

Especially Preference is given to mixtures of the diacid dichlorides of isophthalic acid and terephthalic acid in the ratio between 1:20 and 20: 1.

at the production of polyester carbonates is in addition a carbonic acid halide, preferably phosgene, as a bifunctional Acid derivative with used.

As chain terminators for the preparation of the aromatic polyester are in addition to the aforementioned monophenols still their chloroformate and the acid chlorides of aromatic monocarboxylic acids, which may be substituted by C ₁ to C ₂₂ alkyl groups or by halogen atoms, and aliphatic C ₂ to C ₂₂ monocarboxylic acid chlorides into consideration.

The Amount of chain terminators is 0.1 to 10 mol% in each case, in the case of phenolic chain terminators based on moles of diphenol and in the case of monocarboxylic acid chloride chain terminators on moles of dicarboxylic acid dichloride.

The aromatic polyester carbonates may also be aromatic Hydroxycarboxylic acids incorporated included.

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 ).

Examples of suitable branching agents are trifunctional or polyfunctional carboxylic acid chlorides, such as trimesic acid trichloride, cyanuric trichloride, 3,3 ', 4,4'-benzophenone-tetracarboxylic acid tetrachloride, 1,4,5,8-naphthalene tetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride, in amounts of 0.01 to 1.0 mol% (based on dicarboxylic acid dichlorides used) or trifunctional or polyfunctional phenols, such as Phlo roglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hept-2-ene, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzene, 1,1,1-tri- (4-hydroxyphenyl) -ethane, tri- (4-hydroxyphenyl) -phenylmethane, 2,2-bis [4, 4-bis (4-hydroxy-phenyl) -cyclohexyl] -propane, 2,4-bis (4-hydroxyphenyl-isopropyl) -phenol, tetra (4-hydroxyphenyl) -methane, 2,6-bis (2-hydroxy 5-methyl-benzyl) -4-methyl-phenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) -propane, tetra- (4- [4-hydroxyphenyl-isopropyl] -phenoxy) - methane, 1,4-bis [4,4'-dihydroxytri-phenyl) -methyl] -benzene, in amounts of 0.01 to 1.0 mol% based on diphenols used. Phenolic branching agents can be introduced with the diphenols, acid chloride branching agents can be added together with the acid dichlorides.

In the thermoplastic, aromatic polyester carbonates, the Proportion of carbonate structural units vary as desired. Preferably the proportion of carbonate groups is 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. Either the ester as well as the carbonate content of the aromatic polyester carbonates may be in the form of blocks or randomly distributed in the polycondensate available.

The relative solution viscosity (η _rel ) of the aromatic polycarbonates and polyester carbonates is in the range of 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 25 ° C).

The thermoplastic, aromatic polycarbonates and polyestercarbonates can be used alone or in any mixture.

Component B

• B.1 5 bis 95, vorzugsweise 30 bis 90 Gew.-%, wenigstens eines Vinylmonomeren auf
• B.2 95 bis 5, vorzugsweise 70 bis 10 Gew.-% einer oder mehrerer Pfropfgrundlagen mit einer Glasübergangstemperatur < 10°C, vorzugsweise < 0°C, besonders bevorzugt < -20°C,

dadurch gekennzeichnet, die Reaktion der Komponente B.1 mit der Pfropfgrundlage B.2 mittels Emulsionspolymerisation erfolgt („Pfropfreaktion"), wobei ein Emulgator gemäß Formel (I) eingesetzt wird.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 on
• B.2 95 to 5, preferably 70 to 10 wt .-% of one or more graft bases having a glass transition temperature <10 ° C, preferably <0 ° C, particularly preferably <-20 ° C,

characterized in that the reaction of the component B.1 with the graft B.2 by means of emulsion polymerization ("grafting reaction"), wherein an emulsifier according to formula (I) is used.

The graft base B.2 generally has an average particle size (d ₅₀ value) of 0.05 to 10 .mu.m, preferably 0.1 to 5 .mu.m, particularly preferably 0.2 to 0.8 microns.

• B.1.1 50 bis 99 Gew.-Teilen Vinylaromaten und/oder kernsubstituierten Vinylaromaten (wie Styrol, p-Chlorstyrol) und/oder (Meth)Acrylsäure-(C₁-C₈)-Alkylester, (wie Methylmethacrylat, Ethylmethacrylat), und
• B.1.2 1 bis 50 Gew.-Teilen Vinylcyanide (ungesättigte Nitrile wie Acrylnitril und Methacrylnitril) und/oder (Meth)Acrylsäure-(C₁-C₈)-Alkylester, wie Methyl methacrylat, n-Butylacrylat, t-Butylacrylat, und/oder Derivate (wie Anhydride und Imide) ungesättigter Carbonsäuren, beispielsweise Maleinsäureanhydrid und N-Phenyl-Maleinimid.

Monomers B.1 are preferably mixtures of

• B.1.1 50 to 99 parts by weight of vinylaromatics and / or ring-substituted vinylaromatics (such as styrene, p-chlorostyrene) and / or (meth) acrylic acid (C ₁ -C ₈ ) -alkyl esters, (such as methyl methacrylate, ethyl methacrylate), and
• B.1.2 1 to 50 parts by weight of vinyl cyanides (unsaturated nitriles such as acrylonitrile and methacrylonitrile) and / or (meth) acrylic acid (C ₁ -C ₈ ) alkyl esters, such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and / or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids, for example maleic anhydride and N-phenyl-maleimide.

preferred Monomers B.1.1 are selected from at least one of Monomeric styrene and methyl methacrylate, preferred monomers B.1.2 are selected from at least one of the monomers acrylonitrile, Maleic anhydride and methyl methacrylate. Especially preferred Monomers are B.1.1 styrene and B.1.2 acrylonitrile.

For the graft polymers B suitable graft B.2 are, for example 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 (eg according to B.1.1 and B.1.2), with the Provided that the glass transition temperature of the Component B.2 below <10 ° C, preferably <0 ° C, more preferably <-10 ° C lies. Especially preferred is pure polybutadiene rubber.

The gel content of the graft base B.2 is at least 30% by weight, preferably at least 40 Wt .-% (measured in toluene at 25 ° C).

The Grafting B.2 is free radical polymerization, z. B. by emulsion, suspension, solution or bulk polymerization, preferably prepared by emulsion polymerization.

There in the grafting reaction the grafting monomers are not necessarily known grafted completely onto the grafting base, according to the invention under graft polymers B also understood such products by (co) polymerization the graft monomers are obtained in the presence of the graft and incurred in the workup.

Prefers emulsion graft polymers are used which have a core-shell structure exhibit.

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. Preferred polymerizable acrylic acid esters include C ₁ to C ₈ alkyl esters, for example, methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Haloalkyl, preferably halo-C ₁ -C ₈ alkyl esters, such as chloroethyl acrylate and mixtures of these monomers.

to Crosslinking can be monomers with more than one polymerizable Double bond to be copolymerized. 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 carbon atoms, or saturated polyols with 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; multiple unsaturated heterocyclic compounds, such as trivinyl and triallyl cyanurate; polyfunctional vinyl compounds, such as 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 containing at least three ethylenically unsaturated Have groups. Particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloylhexahydro-s-triazine, Trivinylbenzene. The crosslinking monomers can be used individually, but also be used in mixtures. The amount of networking Monomers is preferably 0.02 to 5, in particular 0.05 to 2 wt .-%, based on the graft B.2. In cyclic crosslinking monomers having at least three ethylenically unsaturated Groups, it is advantageous, 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 B.2 are, for. As acrylonitrile, styrene, α-methylstyrene, (meth) acrylamides, vinyl-C ₁ -C ₆ -alkyl ether, methyl methacrylate, butadiene. Preferred acrylate rubbers as the graft base B.2 are emulsion polymers which have a gel content of at least 40% by weight (measured in toluene at 25 ° C.).

Further suitable grafting principles according to B.2 are silicone gums with graft-active sites as described in US Pat DE-OS 3 704 657 . DE-OS 3 704 655 . DE-OS 3 631 540 and DE-OS 3 631 539 to be discribed.

The gel content of the graft base B.2 is determined at 25 ° C. in a suitable solvent ( M. Hoffmann, H. Krämer, R. Kuhn, Polymer Analytics I and II, Georg Thieme-Verlag, Stuttgart 1977 ).

The average particle size d ₅₀ is the diameter, above and below which each 50 wt .-% of the particles are. He can by means of Ultrazentrifugenmessung ( W. Scholtan, H. Lange, colloid. Z. and Z. Polymere 250 (1972), 782-796 ).

Out the prior art is known that the graft B.2 be prepared by the process of emulsion polymerization can. Usually polymerized at 20 ° C. to 100 ° C, preferably at 30 ° C to 80 ° C. As a rule, customary anionic emulsifiers are used, for example, alkali metal salts of alkyl or alkylaryl sulfonic acids, Alkyl sulfates, fatty alcohol sulfonates, salts of higher carboxylic acids with 10 to 30 carbon atoms, sulfosuccinates, ether sulfonates or resin soaps. Usually one takes the alkali metal salts, in particular the Na and K salts, of alkyl sulfonates, sulfosuccinates, fatty acids or carboxylic acids having 10 to 30 carbon atoms.

The choice of the emulsifier for the preparation of the rubber base in the present invention depends on the criteria known to those skilled in the art, such as e.g. Latex shear stability and texture of latex particles, particle size, particle size distribution, viscosity, residual monomer content, gel content and thus contrary to the doctrine of EP-A 0 900 827 not dependent on the exclusion of components which decompose the polycarbonate. According to the present invention z. 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 in DE 3 639 904 A1 described), alkali metal salts of alkyl or aryl sulfates or sulfonates or alkali metal salts of sulfosuccinates. Emulsifier mixtures and combinations of ionic and nonionic emulsifiers may also be used in the manner known to those skilled in the art.

In usually 0.1 to 10 wt .-%, preferably 0.2 to 5 wt .-%, particularly preferably 0.3 to 2.5 wt .-% emulsifier based on the Sum of used for the preparation of the rubber base Monomers used.

For the preparation of the emulsion graft polymer B used for the polycarbonate compositions according to the invention, the choice of emulsifier is crucial in the grafting reaction. It has surprisingly been found that not all common emulsifiers can be used in the grafting reaction, as z. In WO 99/01489 A1 be described in the production of graft polymers for particularly light ABS molding compositions. In order to achieve the object according to the invention, only the anionic emulsifiers according to formula (I) are suitable in the grafting reaction.

wobei
R⁹ und Y^- die oben erläuterte Bedeutung haben,
EWG unabhängig voneinander die oben erläuterte Bedeutung haben,
F eine Alkyliden-Gruppe -CR¹⁰R¹¹- darstellt, wobei
R¹⁰ und R¹¹ unabhängig voneinander jeweils H, Alkyl-, Cycloalkyl-, (Aryl)alkyl-, (Alkyl)aryl-, Alkoxy- oder Aryloxygruppe mit 1 bis 30 Kohlenstoffatomen darstellen, bevorzugt H, Methyl, Ethyl, Propyl, Butyl, Pentyl, Cyclopentyl, Hexyl, Cyclohexyl, Heptyl, Cycloheptyl, Octyl, Nonyl, Decyl, Undecyl, Dodecyl, Tridecyl, besonders bevorzugt sind R¹⁰ = R¹¹ = HIn a preferred embodiment for the preparation of the component B of the polycarbonate compositions according to the invention, an anionic emulsifier of the formula (V) is used in the grafting reaction,

in which
R ⁹ and Y ^{- have} the meaning explained above,
Independently of one another have the meaning explained above,
F represents an alkylidene group -CR ¹⁰ R ¹¹ -, wherein
R ¹⁰ and R ¹¹ independently of one another each represent 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, heptyl, cycloheptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, more preferably R ¹⁰ = R ¹¹ = H

wobei
R¹² und R¹³ unabhängig voneinander jeweils H, Alkyl, Cycloalkyl, (Aryl)alkyl oder Alkyl(aryl) mit 1 bis 30 Kohlenstoffatomen, vorzugsweise 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, mit C₁ bis C₃₀-Alkyl substituiertes Phenyl (wie z. B. Methyl-, Ethyl, Propyl, Butyl-, Pentyl-, Hexyl-, Heptyl-, Octyl-, Nonyl-, Decyl-, Undecyl-, Dodecyl-, (Tridecyl)phenyl), C₂ bis C₁₀₀ ethoxylierte Fettalkoholreste mit 1 bis 130 Kohlenstoffatomen, C₃ bis C₉₉ propoxylierte Fettalkoholreste mit 4 bis 129 Kohlenstoffatomen, C₂ bis C₁₀₀ ethoxylierte (Alkyl)phenolreste mit 3 bis 130 Kohlenstoffatomen, C₃ bis C₉₉ propoxylierte (Alkyl)phenolreste mit 4 bis 129 Kohlenstoffatomen, besonders bevorzugt Propyl, Butyl, Pentyl, Cyclopentyl, Hexyl, Cyclohexyl, Heptyl, Octyl, Nonyl, Decyl, Undecyl, Dodecyl, Tridecyl, insbesondere bevorzugt Hexyl, Cyclohexyl, Heptyl, n-Octyl und 2-Ethylhexyl bedeuten, und
M⁺ ist ausgewählt aus der Reihe der Alkali-Metalle (wie z. B. Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, bevorzugt Na⁺ oder K⁺.In a particularly preferred embodiment for the preparation of the component B of the polycarbonate compositions according to the invention, an anionic emulsifier of the formula (VI) is used in the grafting reaction,

in which
R ¹² and R ¹³ are each independently H, alkyl, cycloalkyl, (aryl) alkyl or alkyl (aryl) of 1 to 30 Koh lenstoffatomen, 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, phenyl substituted with C ₁ to C ₃₀ -alkyl (such as, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, Undecyl, dodecyl, (tridecyl) phenyl), C ₂ to C ₁₀₀ 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 with 3 to 130 carbon atoms, C ₃ to C ₉₉ propoxylated (alkyl) phenol radicals having 4 to 129 carbon atoms, more preferably propyl, butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, especially preferred Hexyl, cyclohexyl, heptyl, n-octyl and 2-ethylhexyl, and
M ⁺ is selected from the group of alkali metals (such as Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , preferably Na ⁺ or K ⁺ .

Some of these emulsifiers are known and commercially available, such as. B. Aerosol ^® OT, Aerosol ^® TR, Aerosol A196 ^® (Aerosol types from. Cytec Industries Inc.) (. Empimin grades from Huntsman), Empimin OT ^®, Empimin ^® OP, 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).

These Emulsifiers can be used individually as well as mixtures with each other, as well as in combination with other, known in the art non-ionic emulsifiers for better stabilization of the dispersion be used.

In a most preferred embodiment for the production Component B of the polycarbonate compositions of the invention is in the grafting reaction as an emulsifier sulfosuccinic Dicyclohexyldiester used.

The Emulsifiers for the grafting reaction in the preparation Component B of the compositions of 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.

Preferably this much is used to prepare the graft polymer dispersion Water, that the final dispersion has a solids content of 20 to 50% by weight.

To the Starting the polymerization reaction, all radical formers are suitable which decay at the selected reaction temperature, ie both those that thermally decompose alone, as well as those who do this in the presence of a redox system. For example it is peroxides, preferably peroxosulphates (such as sodium or potassium peroxodisulphate). However, it is also possible to use redox systems, especially those based on hydroperoxides such as cumene hydroperoxide or tert-butyl hydroperoxide, be used.

In usually the polymerization initiators are in an amount of From 0.05 to 1% by weight, based on the grafting monomers (B.1), used.

The Free radical generator and also the emulsifiers and optionally the in the next paragraph explained molecular weight regulator are the reaction mixture, for example discontinuously as Total at the beginning of the reaction, or divided into several portions in portions at the beginning and one or more later Times added, or continuously during added to a certain time interval. The continuous Addition can also be made along a gradient, the z. For example, or descending, linear or exponential, or even stepwise (Staircase function) can be.

Further can molecular weight regulator such. Ethylhexyl thioglycolate, n- or t-dodecylmercaptan and / or other mercaptans, terpinols and / or dimeric α-methylstyrene and / or others, for control the molecular weight suitable compounds, concomitantly used.

The Molecular weight regulators become discontinuous in the reaction mixture or continuously added, as is the case for the Free radical generator and emulsifiers previously described.

If Molecular weight regulators used in the polymerization, so they can in the preparation of the graft B.2 or in the preparation of the graft B.1 or both in the Preparation of Grafting Base B.2 and Grafting B.1 in be added as described above.

The workup of the dispersion of the emulsion graft polymer B takes place in a person skilled in the art For example, the graft polymer B is initially precipitated from the dispersion, for example by the addition of falling salt solutions (such as calcium chloride, magnesium sulfate, alum) or acids (such as acetic acid Hydrochloric acid or sulfuric acid) or else by freezing (freeze coagulation) or by high shear precipitation (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. The resulting aqueous phase is separated in a conventional manner, for example by sieving, filtering, decanting or centrifuging. After separation of the dispersion water, the water-moist graft polymer is obtained, which usually has a residual water content of up to 60 wt .-%.

there will be no or only a partial separation of excipients, such as z. As emulsifiers, salts, buffer substances, achieved, so that a Substantial amount of up to 100% of the excipients (that is, emulsifiers and other aids) in the graft polymer and thus in the final product remains.

alternative For precipitation, spray drying may be used in which the dispersion is brought to coagulation without first to be converted into fine drops distributed in the air or inert gas is and then in the air or inert gas countercurrent is dried to powder. All excipients remain 100% in the final product.

Component C

The Component C comprises one or more thermoplastic vinyl (co) polymers C.1 and / or polyalkylene terephthalates C.2.

• C.1.1 50 bis 99, vorzugsweise 60 bis 80 Gew.-Teilen Vinylaromaten und/oder kernsubstituierten Vinylaromaten wie Styrol, p-Chlorstyrol) und/oder (Meth)Acrylsäure-(C₁-C₈)-Alkylester, wie Methylmethacrylat, Ethylmethacrylat), und
• C.1.2 1 bis 50, vorzugsweise 20 bis 40 Gew.-Teilen Vinylcyanide (ungesättigte Nitrile) wie Acryl-nitril und Methacrylnitril und/oder (Meth)Acryl-säure-(C₁-C₈)-Alkylester, wie Methylmeth-acrylat, n-Butylacrylat, t-Butylacrylat, und/oder ungesättigte Carbonsäuren, wie Maleinsäure, und/oder Derivate, wie Anhydride und Imide, ungesättigter Carbonsäuren, beispielsweise Maleinsäureanhydrid und N-Phenylmaleinimid).

Suitable as vinyl (co) polymers C.1 polymers of at least one monomer from the group of vinyl aromatics, vinyl cyanides (unsaturated nitriles), (meth) acrylic acid (C ₁ -C ₈ ) alkyl esters, unsaturated carboxylic acids and derivatives (such as anhydrides and imides) of unsaturated carboxylic acids. Particularly suitable are (co) polymers of

• C.1.1 50 to 99, preferably 60 to 80 parts by weight of vinylaromatics and / or ring-substituted vinylaromatics such as styrene, p-chlorostyrene) and / or (meth) acrylic acid (C ₁ -C ₈ ) -alkyl esters, such as methyl methacrylate, ethyl methacrylate ), and
• C.1.2 1 to 50, preferably 20 to 40 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 unsaturated carboxylic acids, such as maleic acid, and / or derivatives, such as anhydrides and imides, unsaturated carboxylic acids, for example, maleic anhydride and N-phenylmaleimide).

The Vinyl (co) polymers C.1 are resinous, thermoplastic and rubber-free. The copolymer of C.1.1 styrene and C.1.2 is particularly preferred Acrylonitrile.

The (Co) polymers according to C.1 are known and leave by radical polymerization, in particular by emulsion, Prepare suspension, solution or bulk polymerization. The (co) polymers preferably have average molecular weights Mw (weight average, determined by light scattering or sedimentation) between 15,000 and 200,000.

The Polyalkylene terephthalates of component C.2 are reaction products from aromatic dicarboxylic acids or their reactive ones 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 and at least 80% by weight, preferably at least 90 mol%, based on the diol component ethylene glycol and / or butanediol-1,4 radicals.

The preferred polyalkylene terephthalates may be in addition to terephthalic acid residues up to 20 mol%, preferably up to 10 mol%, of other aromatic radicals or cycloaliphatic dicarboxylic acids having 8 to 14 carbon atoms or aliphatic dicarboxylic acids having 4 to 12 carbon atoms included, such as B. residues of phthalic acid, isophthalic acid, Naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyl dicarboxylic acid, Succinic acid, adipic acid, sebacic acid, Azelaic acid, cyclohexanediacetic acid.

The preferred polyalkylene terephthalates, in addition to ethylene glycol or butane-1,4-diol residues, may contain up to 20 mol%, preferably up to 10 mol%, of other aliphatic diols of 3 to 12 carbon atoms or cycloaliphatic diols of 6 to 21 carbon atoms. Contain atoms, z. B. residues of 1,3-propanediol, 2-ethylpropane-1,3-diol, neopentyl glycol, pentanediol-1,5, 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-diethylpropanediol-1,3, hexanediol-2,5, 1,4-di (β -hydroxyethoxy) benzene, 2,2-bis (4-hydroxycyclohexyl) propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis (4-β-hydroxyethoxy -phenyl) -propane and 2,2-bis (4-hydroxypropoxyphenyl) -propane ( DE-A 2 407 674 . 2 407 776 . 2,715,932 ).

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. B. according to DE-A 1 900 270 and U.S. Patent 3,692,744 to be branched. Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol.

Especially preferred are polyalkylene terephthalates made from terephthalic acid alone and their reactive derivatives (eg their dialkyl esters) and ethylene glycol and / or 1,4-butanediol have been prepared, and mixtures of these polyalkylene terephthalates.

mixtures of polyalkylene terephthalates contain from 1 to 50% by weight, preferably 1 to 30% by weight, polyethylene terephthalate and 50 to 99% by weight, preferably 70 to 99 wt .-%, polybutylene terephthalate.

The Polyalkylene terephthalates preferably used generally have an intrinsic viscosity of 0.4 to 1.5 dl / g, preferably 0.5 to 1.2 dl / g, measured in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C in Ubbelohde viscometer.

The polyalkylene terephthalates can be prepared by known methods (see, for example, US Pat. Plastics Handbook, Volume VIII, p. 695 ff., Carl-Hanser-Verlag, Munich 1973 ).

Component D

phosphorus Flame retardant (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, which also include mixtures of several components selected from one or more of these groups can be used as a flame retardant. Others here too not specifically mentioned halogen-free phosphorus compounds can be alone or in any combination with others halogen-free phosphorus compounds are used.

worin
R¹, R², R³ und R⁴ unabhängig voneinander C₁ bis C₈-Alkyl, C₅ bis C₆-Cycloalkyl, C₆ bis C₂₀-Aryl oder C₇ bis C₁₂-Aralkyl bedeuten, die jeweils mit Alkyl, vorzugsweise C₁ bis C₄-Alkyl, und/oder Halogen, vorzugsweise Chlor, Brom substituiert sein können,
n unabhängig voneinander 0 oder 1, vorzugsweise ist n = 1,
q 0 bis 30 und
X einen ein- oder mehrkernigen aromatischen Rest mit 6 bis 30 C-Atomen oder einen linearen oder verzweigten aliphatischen Rest mit 2 bis 30 C-Atomen, der OH-substituiert sein und bis zu 8 Etherbindungen enthalten kann, bedeuten.Preferred mono- and oligomeric phosphoric or phosphonic acid esters are phosphorus compounds of the general formula (VII)

wherein
R ¹ , R ² , R ³ and R ⁴ independently of one another are C ₁ to C ₈ -alkyl, C ₅ to C ₆ -cycloalkyl, C ₆ to C ₂₀ -aryl or C ₇ to C ₁₂ -aralkyl, each being alkyl , preferably C ₁ to C ₄ -alkyl, and / or halogen, preferably chlorine, bromine may be substituted,
n are independently 0 or 1, preferably n = 1,
q 0 to 30 and
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.

oder deren chlorierte oder bromierte Derivate, insbesondere leitet sich X von Resorcin,
Hydrochinon, Bisphenol A oder Diphenylphenol ab; besonders bevorzugt leitet sich X von Bisphenol A ab.Preferably, R ¹ , R ² , R ³ and R ^{4 are} independently C ₁ to C ₄ alkyl, phenyl, naphthyl or phenyl-C ₁ -C ₄ alkyl. The aromatic groups R ¹ , R ² , R ³ and R ⁴ may in turn be substituted by halogen and / or alkyl groups, preferably chlorine, bromine and / or C ₁ to C ₄ -alkyl. Especially 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 1;
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

or their chlorinated or brominated derivatives, in particular X is derived from resorcinol,
Hydroquinone, bisphenol A or diphenylphenol; X is particularly preferably derived from bisphenol A.

When Component D according to the invention can also mixtures of different phosphates can be used.

phosphorus compounds of the formula (VII) are, in particular, tributyl phosphate, triphenyl phosphate, Tricresyl phosphate, diphenyl cresyl phosphate, diphenyloctyl 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 formula (VII) derived from bisphenol A is especially prefers.

The phosphorus compounds according to component D are known (cf. 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 technischen Chemie, Vol. 18, p. 301 ff. 1979 ; Houben-Weyl, Methods of Organic Chemistry, Vol. 12/1, p. 43; Beilstein Vol. 6, p. 177 ).

The mean q values can be determined by using suitable method (Gas Chromatography (GC), High Pressure Liquid Chromatography (HPLC), gel permeation chromatography (GPC)) Composition of the phosphate mixture (molecular weight distribution) is determined and calculated therefrom the mean values for q become.

Furthermore, phosphonatamines and phosphazenes, as described in WO 00/00541 and WO 01/18105 are described, are used as flame retardants.

The Flame retardants can be used alone or in any mixture used with each other or in mixture with other flame retardants become.

Component E

The 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 fluorinated polyolefin, silicone and aramid fiber classes), lubricants and mold release agents (for example pentaerythritol tetrastearate), nucleating agents, stabilizers, antistatic agents (e.g. Carbon fibers, carbon nanotubes and organic antistats 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) and dyes and pigments.

Prefers the acids are selected according to component E. from at least one of the group of aliphatic dicarboxylic acids, the aromatic dicarboxylic acids and the hydroxy-functionalized Dicarboxylic acids. Particularly preferred are citric acid, Oxalic acid, terephthalic acid or mixtures of said Links.

The graft polymers other than component B are prepared by free-radical Polymerization, z. B. by emulsion, suspension, solution or bulk polymerization, wherein in the case of emulsion polymerization an emulsifier other than formula (I) is used. Prefers are different from component B graft polymers by Solution or bulk polymerization are prepared.

Production of the molding compositions and moldings

The thermoplastic molding compositions according to the invention are prepared by the respective ingredients in a known Mixed manner and at temperatures of 200 ° C to 300 ° C. in common units such as internal mixers, extruders and Twin-screw extruders melt-compounded and melt-extruded.

The Mixing of the individual constituents can both in a known manner be done successively as well as simultaneously, both at about 20 ° C (room temperature) as well as at higher temperature.

object The invention likewise provides processes for the preparation of the molding compositions and the use of the molding compositions for the production of moldings as well as the moldings themselves.

The molding compositions according to the invention can Production of moldings of any kind can be used. These can be achieved by injection molding, extrusion and blow molding getting produced. Another form of processing is the manufacture of moldings by deep drawing from previously prepared Plates or foils.

Examples for such moldings are films, profiles, housing parts of every kind, eg For household appliances such as televisions, Juicers, coffee machines, blenders; for office machines such as monitors, flat screens, notebooks, printers, copiers; Plates, Pipes, electrical installation ducts, windows, doors and other profiles for the construction sector (interior design and Outdoor applications) as well as 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.

Especially can the molding compositions of the invention for example, for the production of the following moldings or moldings are used: interior fittings for Rolling stock, ships, aircraft, buses and other motor vehicles, Housings of small transformers containing electrical appliances, Housing for information processing equipment and transmission, housing and paneling of medical equipment, massagers and housings for, toy vehicles for children, flat Wall elements, housing for safety devices and for televisions, thermally insulated Transport containers, moldings for sanitary and bathroom equipment, grille for air openings and housing for garden tools.

The The following examples serve to further explain the Invention.

Examples

Component A

• A.1: Linear polycarbonate based on bisphenol-A with a weight-average molecular weight M _w of 27500 g / mol (determined by GPC in CH ₂ Cl ₂ at 25 ° C).
• 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

B type emulsion graft polymers with polybutadiene rubber base

The particulate crosslinked rubber base used for the preparation of component B (emulsion graft polymer) was prepared by free-radical emulsion polymerization of butadiene in the presence of sodium salt of a special TCD emulsifier, as in DE 39 135 09 A1 (Example 1) is prepared. The polybutadiene bases thus obtained have a mean pond size d ₅₀ = 350 nm and were used in the form of polymer latices in the further reaction step (carried out in each case according to general instructions (I) or (II)).

All Parts by weight in the examples below to graft polymers are standardized so that for each graft polymer indicated below the sum of the parts by weight (parts by weight) of the graft base (Polybutadiene) and the parts by weight of the graft monomers (styrene and Acrylonitrile) gives 100 parts by weight. The amounts of water, emulsifiers, Initiators and other aids refer to this sum the parts by weight of the grafting base and the grafting monomers (= 100 Parts by weight).

General Procedure (I): Preparation the graft polymers B (1.1a) to B (1.2c):

60 parts by weight of polybutadiene (in the form of a latex, which was prepared using the compound TCD emulsifier as an emulsifier, solids content 25 wt .-%, average particle diameter d ₅₀ = 350 nm) and 0-2 parts by weight of each used emulsifier are heated under nitrogen to 65 ° C and treated with 0.5 parts by weight of potassium peroxodisulfate (dissolved in 20 parts by weight of water) and 0.3 parts by weight of sodium hydroxide (dissolved in 20 parts by weight of water) , Thereafter, 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 post-reaction time, the latex is coagulated in a magnesium sulfate / acetic acid solution, filtered off, optionally washed and the resulting powder dried at 70 ° C in a vacuum.

General rule (II): Preparation the graft polymers B (2.1a) to B (2.2e):

60 parts by weight of polybutadiene (in the form of a latex, which was prepared using the compound TCD emulsifier as an emulsifier, solids content 25 wt .-%, average particle diameter d ₅₀ = 350 nm) and 0-2 parts by weight of each used emulsifier are heated to 65 ° C under nitrogen. 0.4 part by weight of tert-butyl hydroperoxide (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 4 hours. In parallel, 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 post-reaction time, 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.

Graft Polymer B (1.1a): Preparation according to general rule (I)

• Emulsifier: 1.5 parts by weight of the sodium salt of sulfosuccinic acid dicyclohexyl diester (Aerosol A196, Cytec Industries).
• Coagulant processing: the product obtained after the precipitation Coagulum is filtered off only (about 20 L filtrate solution) and not washed.

Graft Polymer B (1.1b): Preparation according to general rule (I)

• Emulsifier: 1.5 parts by weight of the sodium salt of sulfosuccinic acid dicyclohexyl diester
• Coagulant processing: the product obtained after the precipitation Coagulum is filtered off and once with a large amount distilled water (i.e., about 20 L per 1 kg of polymer).

Graft Polymer B (1.1c): Preparation according to general rule (I)

• Emulsifier: 1.5 parts by weight of the sodium salt of sulfosuccinic acid dicyclohexyl diester
• Coagulant processing: the product obtained after the precipitation Coagulum is filtered off and carefully (that is, 4 times in slurried distilled water, then filtered off and washed with a large amount of distilled water (total about 80 liters per 1 kg of polymer)).

Graft Polymer B (1.1d): Preparation according to general rule (I)

• Emulsifier: 0.5 part by weight of the sodium salt of sulfosuccinic acid dicyclohexyl diester
• Coagulant processing: the product obtained after the precipitation Coagulum is filtered off and not washed.

Graft Polymer B (1.1e) (Comparison): Preparation according to general procedure (I)

• Emulsifier: no emulsifier used in the grafting step
• Coagulant processing: the product obtained after the precipitation Coagulum is filtered off and carefully (that is, 4 times in slurried distilled water, then filtered off and washed with a large amount of distilled water (total 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 of sodium dodecylsulfate (Aldrich)
• Coagulant processing: the product obtained after the precipitation Coagulum is filtered off and carefully (that is, 4 times in slurried distilled water, then filtered off and washed with a large amount of distilled water (total about 80 liters per 1 kg of polymer)).

Graft Polymer B (1.2b) (Comparison): Preparation according to general procedure (I)

• Emulsifier: 1.0 part by weight of sodium dodecylsulfate (Aldrich)
• Coagulant processing: the product obtained after the precipitation Coagulum is filtered off and carefully (that is, 4 times in slurried distilled water, then filtered off and washed with a large amount of distilled water (total 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 processing: the product obtained after the precipitation Coagulum is filtered off and carefully (that is, 4 times in slurried distilled water, then filtered off and washed with a large amount of distilled water (total about 80 liters per 1 kg of polymer)).

Graft Polymer B (2.1a): Preparation according to general rule (II)

• Emulsifier: 2 parts by weight of the sodium salt of sulfosuccinic acid dicyclohexyl diester (Aerosol A196)
• Coagulant processing: the product obtained after the precipitation Coagulum is filtered off only (about 20 L filtrate solution) and not washed.

Graft Polymer B (2.1b): Preparation according to general rule (II)

• Emulsifier: 2 parts by weight of the sodium salt of sulfosuccinic acid dicyclohexyl diester
• Coagulant processing: the product obtained after the precipitation Coagulum is filtered off and once with a large amount distilled water (i.e., about 20 liters per 1 kg of polymer).

Graft Polymer B (2.1c): Preparation according to general rule (II)

• Emulsifier: 2 parts by weight of the sodium salt of sulfosuccinic acid dicyclohexyl diester
• Coagulant processing: the product obtained after the precipitation Coagulum is filtered off and carefully (that is, 4 times in slurried distilled water, then filtered off and washed with a large amount of distilled water (total about 80 liters per 1 kg of polymer)).

Graft Polymer B (2.1d): Preparation according to general rule (II)

• Emulsifier: 1.5 parts of the sodium salt of sulfosuccinic acid dicyclohexyl diester (Aerosol A196)
• Coagulant processing: the product obtained after the precipitation Coagulum is filtered off only (about 20 L filtrate solution) and not washed.

Graft Polymer B (2.1e): Preparation according to general rule (II)

• Emulsifier: 1.0 part of the sodium salt of sulfosuccinic acid dicyclohexyl diester (Aerosol A196)
• Coagulant processing: the product obtained after the precipitation Coagulum is filtered off only (about 20 L filtrate solution) and not washed.

Graft Polymer B (2.1f): Preparation according to general rule (II)

• Emulsifier: 0.5 part of the sodium salt of sulfosuccinic acid dicyclohexyl diester (Aerosol A196)
• Coagulant processing: the product obtained after the precipitation Coagulum is filtered off only (about 20 L filtrate solution) and not washed.

Graft Polymer B (2.2a) (Comparison): Production according to general rule (II)

• Emulsifier: 2 parts sodium dodecyl sulfate (Aldrich)
• Coagulant processing: the product obtained after the precipitation Coagulum is filtered off only (about 20 L filtrate solution) and not washed.

Graft Polymer B (2.2b) (Comparison): Production according to general rule (II)

• Emulsifier: 2 parts sodium dodecyl sulfate (Aldrich)
• Coagulant processing: the product obtained after the precipitation Coagulum is filtered off and once with a large amount distilled water (about 20 L per 1 kg of polymer) washed.

Graft Polymer B (2.2c) (Comparison): Production according to general rule (II)

• Emulsifier: 2 parts sodium dodecyl sulfate (Aldrich)
• Coagulant processing: the product obtained after the precipitation Coagulum is filtered off and carefully (that is, 4 times in slurried distilled water, then filtered off and washed with a large amount of distilled water (total about 80 liters per 1 kg of polymer)).

Pffropfpolymerisat B (2.2d) (comparison): Production according to general rule (II)

• Emulsifier: 0.5 part sodium dodecyl sulfate (Aldrich)
• Coagulant processing: the product obtained after the precipitation Coagulum is filtered off and carefully (that is, 4 times in slurried distilled water, then filtered off and washed with a large amount of distilled water (total about 80 liters per 1 kg of polymer)).

Pfropffpolymerisat B (2.2e) (comparison): Production according to general rule (II)

• Emulsifier: 1.0 part sodium dodecyl sulfate (Aldrich)
• Coagulant processing: the product obtained after the precipitation Coagulum is filtered off and carefully (that is, 4 times in slurried distilled water, then filtered off and washed with a large amount of distilled water (total about 80 liters per 1 kg of polymer)).

Emulsion graft polymers according to component B based on poly (n-butyl acrylate) rubber base:

For the preparation of the particulate, crosslinked rubber base of poly (n-butyl acrylate) rubber, a seed latex was first prepared by polymerizing 10 parts 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 S ₂ O ₈ ) dissolved in 7.0 parts by weight of water for 3 h at 80 ° C. An acrylate latex having a solids content of 10.0% and a weight-average particle size d ₅₀ = 50 nm was obtained.

10.0 parts by weight of the prepared seed latex (1.0 part by weight based on solid polymer) were together with 145 parts by weight of water, 6.85 parts by weight of n-butyl acrylate monomer and 0.3 parts by weight of the previously dissolved in water sodium salt of sulfosuccinic acid Dicyclohexyldiester (Aerosol A196) submitted and heated to 65 ° C. After reaching 65 ° C were 0.25 parts by weight. Potassium peroxodisulfate dissolved in 12.5 parts by weight. Add water within 5 minutes and then the dosages of monomer solution consisting of 90 parts by weight of n-butyl acrylate, 0.45 parts by weight of trimethyloltriacrylate and 2.70 parts by weight. Allyl methacrylate, as well as a solution consisting of 1.20 parts by weight of aerosol A196, 0.20 parts by weight potassium peroxodisulfate and 24.0 parts by weight water) within 5 hours. After the end of the doses, the temperature was brought to 70 ° C and then a solution of 0.05 parts by weight of potassium peroxodisulfate, dissolved in 2.34 parts by weight of water, added over one hour. Thereafter, it was stirred at 70 ° C for an additional hour. A bimodal acrylate rubber base was obtained as a 35% dispersion (~ 100% conversion) with a weight average particle size d ₅₀ = 450 nm.

For The preparation of the graft polymers was 180 parts by weight of poly (n-butyl acrylate) latex (Solids content 34%) were with 17 parts by weight of water, 0.06 parts by weight of respective emulsifier dissolved in 1.14 parts by weight of water, presented in a flask and under nitrogen to 65 ° C. heated. 0.4 parts by weight of tert-butyl hydroperoxide, 0.54 parts by weight Emulsifier (both components dissolved in 20 parts by weight of water), and 0.5 parts by weight of sodium ascorbate (dissolved in 20 parts by weight Water) are added within 7 hours. Parallel to this will be a mixture of 30 parts by weight of styrene and 10 parts by weight of acrylonitrile metered in 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 ° C in a vacuum.

Pffropffpolymerrisat B (2.3a):

• Emulsifier: 1.5 parts 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 after precipitation Coagulum obtained only filtered off (about 20 L filtrate) and not washed.

Component C

C.1:

Copolymer of 75% by weight of styrene and 25% by weight of acrylonitrile having a weight-average molecular weight M _w of 130 kg / mol (determined by GPC), prepared by the bulk polymerization process.

C.2 (comparison):

Copolymer of 70% by weight of α-methylstyrene and 30% by weight of acrylonitrile having a weight-average molecular weight M _w of 90 kg / mol (determined by GPC), prepared by the bulk polymerization process.

Component D.1

• Bisphenol A diphenyl diphosphate, Reofos BAPP, Greate Lakes

Component E

• E.1: Pentaerythritol tetrastearate as lubricant / release agent
• E.2 phosphite stabilizer, Irganox ^® B 900, Messrs. Ciba Specialty Chemicals
• E.3 citric acid (anhydrous), DSM
• E.4 Poly (perfluoroethylene) PTFE, Polyflon FA-500, Fa. Daikin
• E.5 Boehmite, Pural 200, Fa. Sasol
• E.6 bulk ABS Fa. Nippon A & L, available under the trade name "Santac ^® AT 08".

Production and testing of molding compounds

In a 1.5 L internal kneader, the compositions listed in Tables 1 to 3 are prepared. Table 1: PC / ABS composition without flame retardant component Parts by weight A.1 58 B 18 C.1 24 E.1 0.75 E.2 0.12 E.3 0.1 Table 2: PC / ABS composition with flame retardant component Parts by weight A.2 70.5 B 4.0 D.1 13.0 E.1 0.3 E.2 0.1 E.4 0.5 E.5 0.8 E.6 10.8 Table 3: further PC / ABS composition with flame retardant component Parts by weight A.1 77.3 C.1 3.5 B 7.7 D.1 9.8 E.1 0.4 E.2 0.1 E.4 0.4 E.5 0.8 Table 4: PC / ASA composition component Parts by weight A.1 58 B 18 C 24 E.1 0.75 E.2 0.12 E.3 0.1

As a measure of the resistance to hydrolysis of the compositions thus prepared, the change in the MVR is measured according to ISO 1133 at 260 ° C with a stamping load of 5 kg with a 7-day storage of the granules at 95 ° C and 100% relative humidity. The increase in the MVR value is evaluated (calculated as a percentage here) with respect to the initial MVR value DMVR (hydr.). In order to account for variations in temperature during storage, a control sample was used with each storage, the MVR value of which fluctuated after storage by 50 ml / 10 min and then normalized to exactly 50. The resulting normalization factor was also applied to all MVR measured values of a series of measurements. The normalized value MVR change is referred to as DMVR (hydr., Corr.).

As a measure of processing stability (degradation of the polycarbonate with increased processing conditions) of the compositions thus prepared, the change in the MVR is measured according to ISO 1133 at 260 ° C with a 5 kg punch load with a 15 minute dwell time of the melt with air excluded at a temperature of 300 ° C for non-flame retardant PC / ABS compositions and a 30 minute dwell time of the melt with the exclusion of air at a temperature of 300 ° C.

The determination of the notched impact strength a _k is according to ISO 180 / 1A stirred.

To determine the weld line strength a _nF is in accordance with ISO 179 / 1U measured the impact resistance at the weld line of test specimens of dimensions 80 mm × 10 mm × 4 mm injected on both sides.

The elongation at break is in the tensile test ISO 527 certainly.

In Table 5 (were used, the PC / ABS compositions according to Table 1, d. H. without flame retardant) are results of storage in moist climates (hydrolytic stability) and at 300 ° C (processing stability) summarized.

These results show that the use of specific emulsifiers corresponding to formulas I, V and VI in the grafting step B.1 (preparation of component B (a)) has solved the problem of providing polycarbonate compositions according to the invention having improved hydrolysis resistance:
The inventive 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 This result is surprising in particular because the hydrolysis resistance of Composition 4 (Comparative Example), which contains an ABS prepared emulsifier-free on the grafting step, has a DMVR (hydr.corresponding) of 49% means that the compositions containing the graft polymers according to the invention have at least as good resistance to hydrolysis as the composition comprising a graft polymer prepared without any emulsifier.

The compositions of Comparative Examples 5 to 7 and 13 to 15 which comprise an ABS prepared with sodium dodecylsulfate, ie one known in the art (e.g. EP-A 0 900 827 ), 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 contains no emulsifier. These hydrolysis resistances are significantly worse than those of the polycarbonate compositions according to the invention.

waived on a careful workup of the graft polymers with the emulsifiers described in the prior art (compositions Comparative Examples 11 and 12), there is a dramatic degradation of the polycarbonate, which results from the DMVR (hydr. corr.) values of 140 to 206% is closing.

About that In addition, the compositions of the invention show 1 to 3 and also 8 to 10 a good processing stability, which can be seen from DMVR (proc.) values of 37 to 69% (melt storage at 300 ° C, 15 min).

In the flame retardant PC / ABS compositions of Table 6 (employing the PC / ABS compositions shown in Table 2), it is also found that the object underlying this invention is achieved by the use of specific emulsifiers corresponding to Formulas I, V and VI in the grafting step B.1 (preparation of component B (a)) is dissolved. Thus, compositions 17 to 21 according to the invention from Table 5 only show 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 _k ) , Bindenahtfestigkeit (a _nF ) and the elongation at break.

at the flame-retardant PC / ABS compositions of the table 7 (were used, the PC / ABS compositions according to Table 3), it is also found that the invention Compositions 23-25 advantages over the composition 22 with regard to hydrolysis resistance, processing stability, Notched impact strength, weld line strength and elongation at break exhibit.

The PC / ASA compositions of Table 8 show an analogous behavior: the compositions of the invention have both good hydrolysis resistance and good processing Stability, if no alpha-methylstyrene-containing polymer is used as component C (see prior art DE 698 27 302 T2 ). In composition 27, which has good hydrolysis resistance but contains α-methystyrene-containing SAN as component C, the processing stability to composition 26 according to the invention is markedly reduced.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - EP 0900827 A [0004, 0054, 0122]
• WO 99/01489 A [0005]
• - DE 69734663 T2 [0007]
• EP 0 390081 A [0008]
• - JP 08067789A [0009]
• - DE 69827302 T2 [0010, 0127]
• - DE 1495626 [0015]
• - DE 2232877A [0015]
• - DE 2703376 A [0015]
• - DE 2714544 A [0015]
• - DE 3000610 A [0015]
• - DE 3832396 A [0015]
• - DE 3077934 A [0015]
• - DE 2842005 A [0021]
• US 3,419,634 [0024]
• - DE 3334782 A [0024]
• - DE 2940024 A [0032]
• - DE 3007934A [0032]
• - DE 3704657 A [0050]
• - DE 3704655 A [0050]
• - DE 3631540 A [0050]
• - DE 3631539 A [0050]
• - DE 3639904 A1 [0054]
• WO 99/01489 A1 [0056]
• - DE 2407674A [0080]
• - DE 2407776 [0080]
• - DE 2715932 [0080]
• - DE 1900270 A [0081]
• - US 3692744 [0081]
• EP 0 363 608 A [0091]
• - EP 0640655 A [0091]
• WO 00/00541 [0093]
• WO 01/18105 [0093]
• - DE 3913509 A1 [0105]

Cited non-patent literature

• BS Patty, L. Novak and H. Phan (in "Thermal and hydrolytic stability of polycarbonates / acrylonitrile-butadiene-styrene based blends", Society of Automotive Engineers, Special Publication SP (2005), SP-1960 (Advances in Plastic Components, Processes and Technologies), 145-151) [0002]
• "Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964 [0015]
• M. Hoffmann, H. Kramer, R. Kuhn, Polymer Analysis I and II, Georg Thieme-Verlag, Stuttgart 1977 [0051]
• - W. Scholtan, H. Lange, colloid. Z. and Z. Polymere 250 (1972), 782-796 [0052]
• - Kunststoff-Handbuch, Vol. VIII, p. 695 ff., Carl-Hanser-Verlag, Munich 1973 [0085]
• - Ullmanns Enzyklopadie der technischen Chemie, Vol. 18, p. 301 ff. 1979 [0091]
• - Houben-Weyl, Methods of Organic Chemistry, Vol. 12/1, p. 43; Beilstein Vol. 6, p. 177 [0091]
• - ISO 1133 [0115]
• - ISO 1133 [0116]
• - ISO 180 / 1A [0117]
• - ISO 179 / 1U [0118]
• - ISO 527 [0119]

Claims (10)

Compositions containing A) 10-99 parts by weight of aromatic polycarbonate and / or aromatic polyester carbonate, B) 1-35 parts by weight of rubber-modified graft polymer of B.1 5 to 95% by weight of at least one vinyl monomer on B.2 95 to 5% by weight of one or more graft bases having a glass transition temperature <10 ° C., C) 0-40 parts by weight of vinyl (co) polymer and / or polyalkylene terephthalate, a copolymer of α-methystyrene and acrylonitrile being excluded, D ) 0-50 parts by weight based on the sum of the components A + B + C, phosphorus-containing flame retardant, E) 0-50 parts by weight based on the sum of the components A + B + C, additives, characterized in that Component B is obtainable by reaction of component B.1 with the graft base B.2 by means of emulsion polymerization, wherein an emulsifier according to formula (I) is used,

wherein the EWG is a carbonyl, a carboxyl, a nitrile, a nitro or a sulfone group, W is a group selected from C ₁ - to C ₃₀ -alkyl, C ₁ - to C ₃₀ -cycloalkyl, C ₁ - to C ₃₀ -aryl, C ₁ - to C ₃₀ - (aryl) alkyl, C ₁ - to C ₃₀ - (alkyl) aryl, C ₁ - to C ₃₀ -alkoxy, C ₁ - to C ₃₀ -aryloxy, C ₂ to C ₁₀₀ ethoxylated alkoxy or aryloxy group according to the formula RO- (CH ₂ -CH ₂ -O) _a - with a = 1 to 50 and R = C ₁ - to C ₃₀ -alkyl or C ₁ - to C ₃₀ -Aryl, where all groups mentioned may also be substituted, for. B. by one or more electron-withdrawing groups according to the above definition of EWG, R ^{9 is} H or a C ₁ to C ₃₀ alkyl, C ₁ to C ₃₀ aryl, C ₁ to C ₃₀ - (alkyl) aryl, each also Y ^{- is} selected from the group consisting of borate (-O-BO (OR ⁹ ) ^- ), boronate (-BO (OR ⁹ ) ^- ), nitrate (-O-NO ₂ ^- ), nitro - (-NO ₂ ^- ), sulphate (-O-SO ₃ ^- ), sulphonate (-SO ₃ ^- ), phosphate (-OP (OR ⁹ ) O ₂ ^- ) and phosphonate (-P (OR ⁹ ) O ₂ ^- ), z is the number 1 or 2, and M ^{z + is} selected for z = 1 from the group consisting of Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , ammonium cation, alkylammonium cation (NH _{4 -n} R ⁹ _n ⁺ , where n = 1 to 4), phosphonium cation and alkylphosphonium cation (PH _4-n R ⁹ _n ⁺ , where n = 1 to 4 may be), or for z = 2 is selected from the group consisting of Mg ²⁺ , Ca ²⁺ , Sr ²⁺ and Ba ²⁺ . A composition according to claim 1, characterized in that component B is obtainable by reaction of the component B.1 with the graft B.2 by means of emulsion polymerization, wherein an emulsifier according to formula (V) is used,

wherein R ⁹ , Y ^{- have} the meaning set forth in claim 1, EWG independently of one another have the meaning defined in claim 1, F is an alkylidene group -CR ¹⁰ R ¹¹ -, 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. A composition according to claim 1, characterized in that component B is obtainable by reaction of the component B.1 with the graft base B.2 by means of emulsion polymerization, wherein an emulsifier according to formula (VI) is used,

wherein R ¹² and R ¹³ are each independently H, alkyl, cycloalkyl, (aryl) alkyl or alkyl (aryl) of 1 to 30 carbon atoms, and M ^{+ is} selected from the group consisting of. Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ . Composition according to claim 1, characterized in that component B is available is by reaction of component B.1 with the graft B.2 by emulsion polymerization, wherein as emulsifier sulfosuccinic Dicyclohexyldiester is used Composition according to one of the claims 1 to 4, characterized in that the emulsifiers for the grafting reaction in the preparation of component B in the amounts from 0.1 to 5 wt.% Are used. Compositions according to one of Claims 1 to 5, containing as component D compounds of the formula (VII)

wherein R ¹ , R ² , R ³ and R ^{4 are} independently C ₁ to C ₈ alkyl, C ₅ to C ₆ cycloalkyl, C ₆ to C ₂₀ aryl or C ₇ to C ₁₂ aralkyl, each of Alkyl and / or halogen may be substituted, n is independently 0 or 1, q is 0 to 30 and X is a mononuclear or polynuclear aromatic radical having 6 to 30 carbon atoms or a linear or branched aliphatic radical having 2 to 30 carbon atoms which may be OH-substituted and may contain up to 8 ether bonds. Compositions according to one of the claims 1 to 6, wherein the additives according to component E are selected from at least one of the group from flame retardant synergists, rubber modified from component B Graft polymers, antidripping agents, lubricants and mold release agents, nucleating agents, Stabilizers, antistatic agents, acids, fillers and Reinforcing agents, dyes and pigments: Use of the compositions according to any one of the claims 1 to 7 for the production of moldings. Shaped body containing a composition according to one of claims 1 to 7. Shaped body according to claim 9, characterized in that the shaped body an interior fitting for rail vehicles, ships, aircraft, buses and other motor vehicles, a housing of small transformers containing electrical appliances, a housing for equipment for information processing and transmission, a housing or casing of medical devices or massagers, a toy vehicle for children, a flat wall element, a housing for safety devices or for televisions, a heat-insulated transport container, a molding for sanitary and bathing equipment, a cover for air openings or a housing for garden tools is.