Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • 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
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
  • C08K5/092—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
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
  • C08K5/098—Metal salts of carboxylic 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
  • C08K5/49—Phosphorus-containing compounds
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/02—Flame or fire retardant/resistant
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/02—Homopolymers or copolymers of hydrocarbons
  • C08L25/04—Homopolymers or copolymers of styrene
  • C08L25/08—Copolymers of styrene
  • C08L25/12—Copolymers of styrene with unsaturated nitriles
• • 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

Definitions

• the present invention relates to polycarbonate compositions comprising as impact modifier specific rubber-containing graft polymers prepared by the process of emulsion polymerization, and also to a process for the preparation of these polycarbonate compositions and to the use of the polycarbonate compositions in the production of molded bodies, and to the molded, bodies themselves.
• Polycarbonate compositions comprising graft polymers as impact modifiers can have varying stability to hydrolysis and thermal stress depending on the purity of and the additives in the impact modifier, for example ABS (acrylonitrile-butadiene-styrene terpolymer).
• ABS acrylonitrile-butadiene-styrene terpolymer
• Phan in “Thermal and hydrolytic stability of polycarbonate/acrylonitrile-butadiene-styrene based blends”, Society of Automotive Engineers, [Special Publication] SP (2005), SP-1960 (Advances it), Plastic Components, Processes and Technologies), 145-151) describe polycarbonate compositions which have markedly better hydrolytic stability and thermal stability when they contain mass ABS as modifier than when they contain emulsion ABS as modifier.
• polycarbonate/mass ABS compositions compared with that of the polycarbonate/emulsion ABS compositions
• auxiliary agents such as, for example, emulsifiers, flow improvers, stabilizers, salts, etc., these chemicals also including ones which can lead to decomposition of the polycarbonate.
• a further advantage of polycarbonate/mass ABS compositions is their particularly light inherent color (natural color), which has a particularly favorable effect on tire dyeing of the molded bodies consisting of such compositions.
• compositions containing mass ABS as impact modifier frequently show greater changes in their melt viscosity at high, temperatures (e.g. at 280-300° C.), which are accompanied by impaired processing stability.
• Some polycarbonate compositions containing emulsion graft polymers as impact modifier exhibit some technical advantages over polycarbonate compositions containing mass ABS, for example in respect of then surface quality (gloss), so that it is advantageous to use emulsion graft polymers for some applications. If high hydrolytic and thermal stability are required, high demands must be made of the emulsion graft polymers that are used, such as, for example, in respect of their purity, the working-up process used in their preparation, and the omission of certain auxiliary substances in their preparation.
• EP-A 0 900 827 discloses impact-modified polycarbonate compositions with unproved thermal stability which contain emulsion graft polymers and are substantially free of components that degrade the polycarbonate.
• emulsion graft polymers that is substantially free of components that degrade the polycarbonate it is necessary to omit such components completely at each stage of the emulsion process or to free the prepared emulsion graft polymers of such components completely by an appropriate working-up process, for example by washing after coagulation of the graft dispersion.
• carboxylate-containing auxiliary substances e.g. emulsifiers, buffer solutions, etc
• the polycarbonate compositions known from EP-A 0 900 827 contain emulsion graft polymers of the MBS and ABS type which have been prepared using sulfate- and/or sulfonate-containing emulsifiers. These emulsifiers frequently lead to undesirable discoloration of the molding compositions.
• Emulsion graft polymers of the ABS type which are prepared by means of a wide variety of emulsifiers are known from WO-A 99/01489.
• Conventional carboxylate-containing emulsifiers are mentioned as possible emulsifiers for their preparation.
• This patent specification also teaches how to prepare particularly light colored ABS molding compositions in which the processing and the acrylonitrile content in the graft polymer and in the matrix component (SAN resin) play a particularly important role.
• WO-A 99/01489 especially discloses that the compositions containing emulsion ABS have a particular tendency to yellowing or even to turning brown. This yellowing or turning brown is distinguished by a yellowness index of from greater than 30 to far more than 50.
• the yellowness index is dependent on several factors, inter alia on the rubber and acrylonitrile content of the ABS, on the additives in the emulsion polymerization and in the working up, and optionally on the purification of the graft polymer as well as the processing conditions for the molding compositions and conditions during the production of molded bodies.
• the yellowing or brown discoloration is promoted by high temperatures, as it happens, for example, in the case of processing by injection molding or in the case of blending with additives during compounding on an extruder.
• polycarbonate/ABS compositions having the following improved properties are described: for example, a high degree of flowability combined with high strength, improved processability combined with reduced mould coating during injection molding, improved surface quality, more stable surface gloss and, for example, a lighter natural color than is the case with conventional polycarbonate/ABS compositions.
• a specially developed, highly pure ABS is used in these improved polycarbonate/ABS compositions.
• An object of the present invention was to provide impact-modified polycarbonate molding compositions comprising at least one emulsion graft polymer as an impact modifier.
• Compositions of the present invention are distinguished, inter alia, by a combination of a light natural color, high hydrolytic stability and excellent processing stability.
• Compositions of tire present invention additionally, advantageously fulfill the condition that they comprise an emulsion graft polymer that is prepared in a preparation process that is efficient and advantageous for the environment.
• compositions comprising
• the above-described molding compositions according to the invention accordingly differ from the prior art, inter alia, and in particular in that, that in tire preparation of component B, the step of the purification of the emulsion graft polymer (e.g. by washing the coagulated graft polymer with up to 100-fold amount of water) can preferably be omitted, so that the preparation process for the emulsion graft polymer (component B) is efficient and advantageous for the environment. It has been found, surprisingly, that, even though the emulsifier remains in the resulting graft polymer, the impact-modified polycarbonate compositions according to the invention containing that graft polymer have a good natural color, high hydrolytic stability and excellent processing stability.
• the present invention overcomes the technical disadvantage of the above-mentioned prior art that highly pure impact modifiers generally should be used to produce impact-modified polycarbonate molding compositions having improved properties, and that it must be ensured, in particular, that the compositions are free of carboxylate-containing auxiliary substances.
• This is not necessarily required in connection with the present invention. That is, it is not necessarily required to utilize highly purified impact modifiers and in addition, it is not necessary that all compositions must be free of carboxylate-containing auxiliaries.
• the present invention also provides a process for the preparation of impact-modified polycarbonate molding compositions which have an improved natural color along with the good hydrolytic stability and processing stability of the impact-modified polycarbonate molding wherein the constituents
• Aromatic polycarbonates and/or aromatic polyester carbonates that are suitable according to the invention as component A are known in the literature or can be prepared by processes known in the literature (for the preparation of aromatic polycarbonates see, for example, Schnell, “Chemistry and Physics of Polycarbonates”, Interscience Publishers, 1964, and also 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 see, for example, DE-A 3 077 934).
• the preparation of aromatic polycarbonates is carried out, for example, by reaction of diphenols with carbonoic acid halides, preferably phosgene, and/or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalides, by the interfacial process, optionally using chain terminators, for example monophenols, and optionally using branching agents having a functionality of three or more, for example triphenols or tetraphenols.
• Preparation by a melt polymerization process by reaction of diphenols with, for example, diphenyl carbonate is also possible.
• Diphenols for the preparation of the aromatic polycarbonates and/or aromatic polyester carbonates are preferably those of formula (I)
• Preferred diphenols are hydroquinone, resorcinol, dihyaroxydiphenols, 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 ⁇ , ⁇ -bis-(hydroxy-phenyl)-diisopropylbenzenes and derivatives thereof brominated and/or chlorinated on the ring.
• 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′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy-diphenylsulfone and di- and tetra-brominated or chlorinated derivatives thereof, such as, for example, 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) is particularly preferred.
• the diphenols can be used on their own or in the form of any desired mixtures.
• the diphenols are known in the literature or obtainable by processes known in the literature.
• Suitable chain terminators for the preparation of the thermoplastic, aromatic polycarbonates are, for example, phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, and also long-chained 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 from 8 to 20 carbon atoms in the alkyl substituents, such as 3,5-di-tert butylphenol, p-isooctylphenol, 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 from 0.5 mol % % to
• thermoplastic, aromatic polycarbonates have mean weight-average molecular weights (M w , measured, for example, by GPC, ultracentrifugation or scattered light measurement) of from 10,000 to 200,000 g/mol, preferably from 15,000 to 80,000 g/mol, particularly preferably from 24,000 to 32,000 g/mol.
• thermoplastic, aromatic polycarbonates can be branched in a known manner, preferably by incorporating from 0.05 to 2.0 mol %, based on the sum of the diphenols used, of compounds having a functionality of three or more, for example those having three or more phenolic groups.
• copolycarbonates Both homopolycarbonates and copolycarbonates are suitable.
• component A it is also possible to use from 1 to 25 wt. %, preferably from 2.5 to 25 wt. %, based on the total amount of diphenols to be used, of polydiorganosiloxanes having hydroxyaryloxy end groups. These are known (U.S. Pat. No. 3,419,634) and can be prepared by processes known in the literature. The preparation of polydiorganosiloxane-containing copolycarbonates is described in DE-A 3 334 782.
• Preferred polycarbonates in addition to tire homopolycarbonates of bisphenol A, are the copolycarbonates of bisphenol A with up to 15 mol %, based on the molar sums of diphenols, of diphenols other than those mentioned as being preferred or particularly preferred, 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′-dicarboxylic acid and naphthalene-2,6-dicarboxylic acid.
• a carbonic acid halide preferably phosgene, is additionally used concomitantly as bifunctional acid derivative.
• chain terminators for the preparation of the aromatic polyester carbonates also the chlorocarbonic acid esters of the mentioned monophenols as well as the acid chlorides of aromatic monocarboxylic acids, which can optionally be substituted by C 1 - to C 22 -alkyl groups or by halogen atoms, as well as aliphatic C 2 - to C 22 monocarboxylic acid chlorides.
• the amount of chain terminators is in each case from 0.1 to 10 mol %, based in the case of phenolic chain terminators on moles of diphenol and in the case of monocarboxylic acid chloride chain terminators on moles of dicarboxylic acid dichloride.
• the aromatic polyester carbonates can also contain aromatic hydroxycarboxylic acids incorporated therein.
• the aromatic polyester carbonates can be both linear and branched in known manner (see in this connection DE-A 2 940 024 and DE-A 3 007 934).
• branching agents there can be used, for example, carboxylic acid chlorides having a functionality of three or more, such as trimesic acid trichloride, cyanuric acid trichloride, 3,3′-4,4′-benzophenone-tetracarboxylic acid tetrachloride, 1,4,5,8-naphthalenetetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride, in amounts of from 0.01 to 1.0 mol % (based on dicarboxylic acid dichlorides used), or phenols having a functionality of three or more, such as phloroglucinol, 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-
• the amount of carbonate structural units in the thermoplastic, aromatic polyester carbonates can vary as desired.
• the amount 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 esters and the carbonates contained in the aromatic polyester carbonates can be present in the polycondensation product in the form of blocks or randomly distributed.
• the relative solution viscosity ( ⁇ rel ) of the aromatic polycarbonates and polyester carbonates is in the range from 1.18 to 1.4, preferably from 1.20 to 1.32 (measured on solutions of 0.5 g of polycarbonate or polyester carbonate in 100 ml of methylene chloride solution at 25° C.).
• thermoplastic, aromatic polycarbonates and polyester carbonates can be used on their own or in any desired mixture.
• Component B comprises one or more graft polymers of
• the graft base B.2 generally has a mean particle size (d 50 value) of from 0.05 to 10 ⁇ m, preferably from 0.1 to 5 ⁇ m, particularly preferably from 0.2 to 0.8 ⁇ m.
• Monomers B.1 are preferably mixtures of
• Preferred monomers B.1.1 are selected from at least one of the monomers styrene, ⁇ -methylstyrene 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.
• Graft bases B.2 suitable for the graft polymers B are, for example, diene rubbers, EP(D)M rubbers, that is to say those based on ethylene/propylene and optionally a diene, acrylate, polyurethane, silicone, chloroprene and ethylene/vinyl acetate rubbers.
• Preferred graft bases B.2 are diene rubbers, for example based on butadiene and isoprene, or mixtures of diene rubbers or copolymers of diene rubbers or mixtures thereof with further copolymerizable monomers (e.g. according to B.1.1 and B.1.2), with the proviso that the glass transition temperature of component B.2 is below ⁇ 10° C., preferably ⁇ 0° C., particularly preferably ⁇ 10° C. Pure polybutadiene rubber is particularly preferred.
• the gel content of the graft base B.2 is at least 30 wt. %, preferably at least 40 wt. % (measured in toluene at 25° C.).
• the graft base B.2 is prepared by polymerization, for example by emulsion, suspension, solution or mass polymerization, preferably by emulsion polymerization.
• graft polymers B according to the invention are also to be understood as being products that are obtained by (co)polymerization of the graft monomers in the presence of the graft base and that are obtained concomitantly during working up.
• Suitable acrylate rubbers according to B.2 for the polymers B are preferably polymers of acrylic acid alkyl esters, optionally with up to 40 wt. %, based on B.2, of other polymerizable, ethylenically unsaturated monomers.
• the preferred polymerizable acrylic acid esters include C 1 - to C 8 -alkyl esters, for example methyl, ethyl, butyl, n-octyl and 2-ethylhexyl ester; haloalkyl esters, preferably halo-C 1 -C 8 -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 from 3 to 8 carbon atoms and unsaturated monohydric alcohols having from 3 to 12 carbon atoms, or saturated polyols having from 2 to OH groups and front 2 to 20 carbon 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 tri-vinylbenzenes; but also triallyl phosphate and diallyl phthalate.
• crosslinking monomers are allyl (methacrylate, ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, diallyl phthalate and heterocyclic compounds which contain at least three ethylenically unsaturated groups.
• Particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloylhexahydro-s-triazine, trivinylbenzenes.
• the crosslinking monomers can be used individually but also in mixtures.
• the amount of crosslinking monomers is preferably from 0.02 to 5 wt. %, in particular from 0.05 to 2 wt.
• % based on the graft base B.2.
• Preferred “other” polymerizable, ethylenically unsaturated monomers which can optionally be used, in addition to the acrylic acid esters, in 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 graft base B.2 are emulsion polymers having a gel content of at least 40 wt. % (measured in toluene at 25° C.).
• graft bases according to B.2 are silicone rubbers having graft-active sites, as are described in DE-OS 3 704 657, DE-OS 3 704 655, DE-OS 3 631 540 and DE-OS 3 631 539.
• the gel content of the graft base B.2 is determined at 25° C. in a suitable solvent (e.g. toluene) (M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik I und II, Georg Thierne-Verlag, Stuttgart 1977).
• a suitable solvent e.g. toluene
• the mean particle size d 50 is the diameter above and below which in each case 50 wt. % of the particles lie. It can be determined by means of ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid. Z. und Z. Polymere 250 (1972), 782-796).
• Component B is obtainable by the following process:
• the graft base B.2 can be prepared by the process of emulsion polymerization.
• the polymerization is conventionally carried out at from 20° C. to 100° C., preferably from 30° C. to 80° C.
• Conventional anionic emulsifiers are generally used, for example alkali metal salts of alkyl- or alkylaryl-sulfonic acids, alkyl sulfates, fatty alcohol sulfonates, salts of higher carboxylic acids having from 10 to 50 carbon atoms, sulfosuccinates, ether sulfonates or resinates.
• alkali metal salts in particular the Na and K salts, of alkyl sulfates, alkyl sulfonates, sulfosuccinates, fatty acids or carboxylic acids having from 10 to 30 carbon atoms are conventionally taken.
• the choice of emulsifier for the preparation of the rubber base (component B.2) is dependent on the criteria known to the person skilled in the art, such as, for example, the latex shear stability and the properties of the latex particles, particle size, particle size distribution, viscosity, residual monomer content, gel content, and accordingly, contrary to the teaching of EP-A 0 900 827, is not dependent on the exclusion of components that decompose tire polycarbonate.
• component B-2 is prepared using ionic emulsifiers, preferably alkali metal salts of alkyl- or alkylaryl-sulfonic acids, alkyl sulfates, fatty alcohol sulfonates, salts of higher carboxylic acids having from 10 to 50 carbon atoms, sulfosuccinates, ether sulfonates or resinates, particularly preferably alkali metal salts of resin acids, alkali metal salts of higher fatty acids having from 10 to 30 carbon atoms, alkali metal salts of specific dicarboxylic acids (as described, for example, in DE 3 639 904 A1), or mixtures of ionic and non-ionic emulsifiers, in a manner known to the person skilled in the art.
• ionic emulsifiers preferably alkali metal salts of alkyl- or alkylaryl-sulfonic acids, alkyl sulfates, fatty alcohol sulfonates, salt
• emulsifier In general, from 0.1 to 10 parts by weight, preferably from 0.2 to 5 parts by weight, particularly preferably from 0.3 to 2.5 parts by weight, of emulsifier are used, based on the sum of the parts by weight of the monomers used for the preparation of the rubber base.
• emulsifier in the graft reaction is critical for the preparation of the emulsion graft polymer B used for the polycarbonate compositions according to the invention. It has been found, surprisingly, that not all conventional emulsifiers as are described, for example, in WO 99/01489A1 for the preparation of graft, polymers for specific light ABS molding compositions can be used in the graft reaction. In order to achieve the object according to the invention only at least one emulsifier selected from the group consisting of alkali, alkaline earth, ammonium and phosphonium salts of a saturated fatty acid having from 10 to 50 carbon atoms is to be used in die graft reaction. Of course, these emulsifiers can be used from the outset in the preparation of the graft base (see 1st step above), so that it may optionally be possible to omit their addition at the graft polymerization stage.
• alkali metal salt of a saturated monocarboxylic fatty acid having from 10 to 30 carbon atoms particular preference being given to alkali metal salts of the following acids: capric acid (C 9 H 19 COOH), lauric acid (C 17 H 23 COOH), myristic acid (C 13 H 27 COOH), palmitic acid (C 15 H 31 COOH), margaric acid (C 16 H 33 COOH), stearic acid (C 17 H 35 COOH), arachic acid (C 19 H 39 )COOH), behenic acid (C 21 H 43 COOH), lignoceric acid (C 23 H 47 COOH) or cerotic acid (C 25 H 51 COOH).
• the mentioned emulsifiers can also be used in the form of a mixture.
• sodium or potassium salts of saturated monocarboxylic fatty acids having from 12 to 18 carbon atoms are used in the graft reaction, preferably C 17 H 35 COONa or C 17 H 35 COOK.
• emulsifiers can be used either individually or in the form of mixtures with one another as well as in combination with other non-ionic emulsifiers known to the person skilled in the art for the purpose of better stabilization of the dispersion.
• the emulsifiers for the graft reaction are used in amounts of from 0.1 to 5 parts by weight, preferably from 0.3 to 2.5 parts by weight, even more favorably 0.5 to 2.5 parts by weight, in particular 1.0 to 2.5 parts by weight, particularly preferably from 1.5 to 2.5 parts by weight, based on the sum of the parts by weight of the monomers B.1 and graft base B.2 used in the preparation of the graft polymer B.
• Suitable radical formers for starting the polymerization reaction are all radical formers that decompose at the chosen reaction temperature, that is to say both those which decompose solely thermally and those which do so in the presence of a redox system, and preference is given as radical formers to peroxides, preferably peroxosulfates (for example sodium Or potassium peroxodisulfate) or redox systems, in particular those based on hydroperoxides such as cumene hydroperoxide or tert-butyl hydroperoxide.
• the polymerization initiators are used in an amount of from 0.05 to 1 wt. %, based on the graft support monomers (B.1).
• molecular weight regulators such as, for example, ethylhexyl thioglycolate, n- or tert-dodecylmercaptan and/or other mercaptans, terpinols and/or dimeric ⁇ -methylstyrene and/or other compounds suitable for adjusting the molecular weight.
• component B.2 is dispersed in water, if component B.2 is not present in the form of an aqueous dispersion after the preparation, or is diluted with water.
• the amount of water used to prepare the graft polymer dispersion is preferably such that the resulting dispersion has a solids content of from 20 to 50 wt. % when the graft reaction is complete.
• the radical formers, emulsifiers and, optionally, molecular weight regulators are added to the graft polymer dispersion.
• auxiliary substances i.e. radical formers, emulsifiers and molecular weight regulators
• the continuous addition of the auxiliary substances can also be carried out along a gradient (in dependence on time), which can be, for example, increasing or decreasing, linear or exponential, or stepwise.
• molecular weight regulators are used in the polymerization, they can be added in the manner described above in the preparation of the graft base B.2 or in the preparation of the graft support B.1 or both in the preparation of the graft base B.2 and of the graft base B.1, for example discontinuously as a total amount at the beginning of the reaction, or divided into a plurality of portions and added in portions at the beginning and at one or more subsequent stages, or continuously over a specific period of time.
• the continuous addition of the auxiliary substances can also be carried out along a gradient, which can be, for example, increasing or decreasing, linear or exponential, or stepwise.
• buffer substances such as Na 2 HPO 4 /NaH 2 PO 4 , sodium hydrogen carbonate or simple acids, such as, for example, acetic acid, or lyes, such as, for example, NaOH, KOH, can be used concomitantly.
• Working up is carried out by means of spray drying or by means of precipitation and separation of the dispersing water.
• the dispersion In the case of spray drying, the dispersion is converted into fine drops distributed in the air or inert gas, without being made to coagulate beforehand, and is then dried in a counter-stream of air or inert gas to give a powder. Consequently, 100% of all the auxiliary substances remain in the end product.
• the graft polymer B is, for example, first precipitated from the dispersion, for example by addition of salt solutions (for example calcium chloride, magnesium sulfate, alum) or acids (for example acetic acid, hydrochloric acid, phosphoric acid or sulfuric acid) having a precipitating action or alternatively by freezing (freeze coagulation) or by coagulation by means of high shear forces (so-called shear precipitation), the high shear forces being produced, for example, by rotor/stator systems or by pressing the dispersion through a narrow gap.
• the graft polymer B is precipitated from the dispersion by addition of magnesium sulfate, particularly preferably by addition of magnesium sulfate/acetic acid solution, as agent having a precipitating action.
• aqueous phase is separated off in the conventional manner, for example by sieving, filtration, decantation or centrifugation. After separating off the dispersing water, a moist graft polymer is obtained, which usually has a residual water content of up to 60 wt. %.
• the moist graft polymer according to the invention is not washed with water.
• the auxiliary substances such as, for example, emulsifiers, decomposition products of the radical formers, buffer substances, so that a considerable portion of up to 100% of the auxiliary substances remains in the graft polymer and consequently in the end product, that is to say the moist graft polymer.
• the pH value in the working up of the graft polymer dispersion in the step of spray drying (3.1) or precipitation (3.2.1) can be adjusted by processes known to the person skilled in the art, for example by addition of buffer solutions or mineral acids, preferably by addition of one or more acids selected from the group consisting of sulfuric acid, phosphoric acid, nitric acid and C 1 - to C 8 -carboxylic acids (e.g. acetic acid).
• Whether the composition according to the invention must contain acidic additives according to component E depends on the pH value during the working up of the graft polymer dispersion in the step of spray drying or precipitation:
• Component C comprises one or more thermoplastic vinyl (co)polymers C.1 and/or polyalkylene terephthalates C.2.
• Suitable as vinyl (copolymers C.1 are polymers of at least one monomer from the group of the vinyl aromatic compounds, vinyl cyanides (unsaturated nitriles), (meth)acrylic acid (C 1 -C 8 )-alkyl esters, unsaturated carboxylic acids and also derivatives (such as anhydrides and imides) of unsaturated carboxylic acids. Particularly suitable are (co)polymers of
• the vinyl (co)polymers C.1 are resin-like, thermoplastic and rubber-free.
• the copolymer of C.1.1 styrene and C.1.2 acrylonitrile is particularly preferred.
• the (co)polymers according to C.1 are known and can be prepared by radical polymerization, in particular by emulsion, suspension, solution or mass polymerization.
• the (co)polymers preferably have mean molecular weights Mw (weight average, determined by light scattering or sedimentation) of from 15,000 to 200,000.
• the polyalkylene terephthalates of component C.2 are reaction products of aromatic dicarboxylic acids or reactive derivatives thereof, 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 component, of terephthalic acid radicals and at least 80 wt. %, preferably at least 90 mol %, based on the diol component, of ethylene glycol and/or 1,4-butanediol radicals.
• the preferred polyalkylene terephthalates can contain, in addition to terephthalic acid radicals, up to 20 mol %, preferably up to 10 mol %, of radicals of other aromatic or cycloaliphatic dicarboxylic acids having from 8 to 14 carbon atoms or aliphatic dicarboxylic acids having from 4 to 12 carbon atoms, such as, for example, 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.
• radicals of phthalic acid isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4′-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohex
• the preferred polyalkylene terephthalates can contain, in addition to ethylene glycol or 1,4-butanediol radicals, up to 20 mol %, preferably up to 10 mol %, of other aliphatic diols having from 3 to 12 carbon atoms or cycloaliphatic diols having from 6 to 21 carbon atoms, for example radicals of 1,3-propanediol, 2-ethyl-1,3-propanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, cyclohexane-1,4-dimethanol, 3-ethyl-2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,2-diethyl-1,3-
• the polyalkylene terephthalates can be branched by the incorporation of relatively small amounts of tri- or tetra-hydric alcohols or tri- or tetra-basic carboxylic acids, for example according to DE-A 1 900 270 and U.S. Pat. No. 3,692,744.
• preferred branching agents are trimesic acid, trimellitic acid, trimethylol-ethane and -propane and pentaerythritol.
• polyalkylene terephthalates which have been prepared solely from terephthalic acid and reactive derivatives thereof (e.g. dialkyl esters thereof) and ethylene glycol and/or 1,4-butanediol, and mixtures of these polyalkylene terephthalates.
• Mixtures of polyalkylene terephthalates contain from 1 to 50 wt. %, preferably from 1 to 30 wt. %, polyethylene terephthalate and from 50 to 99 wt. %, preferably from 70 to 99 wt. %, polybutylene terephthalate.
• the polyalkylene terephthalates that are preferably used generally have a limiting viscosity of from 0.4 to 1.5 dl/g, preferably from 0.5 to 1.2 dl/g, measured in phenol/o-dichlorobenzene (1:1 parts by weight) at 25° C. in an Ubbelohde viscometer.
• the polyalkylene terephthalates can be prepared by known methods (see e.g. Kunststoff-Handbuch, Volume VIII, p. 695 ff, Carl-Hanser-Verlag, Kunststoff 1973).
• Phosphorus-containing flameproofing agents (component D) within the scope of the invention are preferably selected from the groups of the monomeric and oligomeric phosphoric and phosphonic acid esters, phosphonate amines and phosphazenes, it also being possible to use as flameproofing agents mixtures of several components selected from one or various of these groups.
• Halogen-free phosphorus compounds not mentioned specifically here can also be used on their own or in any desired combination with other halogen-free phosphorus compounds.
• Preferred monomeric and oligomeric phosphoric or phosphonic acid esters are phosphorus compounds of the general formula (IV)
• R 1 , R 2 , R 3 and R 4 independently of one another, preferably represent 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 can in turn be substituted by halogen and/or alkyl groups, preferably chlorine, bromine and/or C 1 - to C 4 -alkyl.
• Particularly preferred aryl radicals are cresyl, phenyl, xylenyl, propylphenyl or butylphenyl and the corresponding brominated and chlorinated derivatives thereof.
• n in formula (I), independently of one another, can be 0 or 1; n is preferably 1.
• Phosphorus compounds of formula (IV) are in particular tributyl phosphate, triphenyl phosphate, tricresyl phosphate, diphenylcresyl phosphate, diphenyloctyl phosphate, diphenyl-2-ethylcresyl phosphate, tri-(isopropylphenyl) phosphate, resorcinol-bridged oligophosphate and bisphenol A-bridged oligophosphate.
• the use of oligomeric phosphoric acid esters of formula (IV) that are derived from bisphenol A is particularly preferred.
• component D is bisphenol A-based oligophosphate according to formula (IVa):
• the phosphorus compounds according to component D are known (see e.g. EP-A 0 363 608, EP-A 0 640 655) or can be prepared by known methods in an analogous manner (e.g. Ullmanns Enzyklopschhe der techthschen Chemie, Vol. 18, p. 301 ff. 1979; Houben-Weyl, Methoden der organischen Chemie, Vol. 12/1, p. 43; Beilstein Vol. 6, p. 177).
• the indicated q value is the mean q value.
• the mean q value can be determined by determining the composition of the phosphorus compound (molecular weight distribution) by means of a suitable method (gas chromatography (GC), high pressure liquid chromatography (HPLC), gel permeation chromatography (GPC)) and calculating the mean values for q therefrom.
• Phosphonate amines and phosphazenes as described in WO 00/00541 and WO 01/18105, can also be used as flameproofing agents.
• the flameproofing agents can be used on their own or in any desired mixture with one another or in admixture with other flameproofing agents.
• the phosphorus-containing flameproofing agents according to component D contain traces of acid (e.g. phosphoric acid, acidic phosphoric acid esters), which can be quantified by acid number (in mg KOH/g of substance) by titration with KOH and are conventionally in the range from 0.01 to 1 mg KOH/g of substance, preferably from 0.02 to 0.5 mg KOH/g of substance and particularly preferably from 0.03 mg KOH to 0.3 mg KOH/g of substance.
• acid number in mg KOH/g of substance
• the acidic additives according to component E are preferably selected from at least one of the group of the aliphatic mono- and di-carboxylic acids, the aromatic mono- and di-carboxylic acids, the hydroxy-functionalized dicarboxylic acids, phosphoric acid, acidic phosphoric acid sodium or potassium salts. Preference is given to citric acid, oxalic acid, terephthalic acid or mixtures of the mentioned compounds. Citric acid is particularly preferred.
• composition can comprise further commercially available additives according to component F, such as flameproofing synergists, rubber-modified graft, polymers other than those of component B, antidripping agents (for example compounds of the substance classes of the fluorinated polyolefins, of the silicones and aramid fibres), lubricants and mould release agents (for example pentaerythritol tetrastearate), nucleating agents, stabilizers, antistatics (for example conductive blacks, carbon fibers, carbon nanotubes and also organic antistatics such as polyalkylene ethers, alkyl sulfonates or polyamide-containing polymers), acids, fillers and reinforcing agents (for example glass or carbon fibers, mica, kaolin, talc, CaCO 3 and flakes) as well as colorings and pigments.
• additives for example compounds of the substance classes of the fluorinated polyolefins, of the silicones and aramid fibres
• the graft polymers other than those of component B are prepared by radical polymerization, for example by emulsion, suspension, solution or mass polymerization, wherein there is used in the case of emulsion polymerization an emulsifier other than alkali metal or ammonium salts of saturated fatty acids. Preference is given to graft polymers other than those of component B that are prepared by solution or mass polymerization.
• thermoplastic molding compositions according to the invention can advantageously be prepared by mixing the constituents in question in a known manner and melt compounding and melt extruding at temperatures of from 260° C. to 300° C. in conventional devices such as internal kneaders, extruders and twin-shaft screws.
• the individual constituents can be mixed in a known manner either in succession or simultaneously, either at about 20° 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 in the production of molded bodies, and the moldings themselves.
• the molding compositions according to the invention can be used, for example, in the production of molded bodies of any kind. These can be produced by injection molding, extrusion and blow molding processes. A further form of processing is the production of molded bodies by deep drawing from previously produced sheets or films.
• molded bodies include films, profiles, casing parts of any kind, for example for domestic appliances such as televisions, juice extractors, coffee machines, mixers; for office machines such as monitors, flat screens, notebooks, printers, copiers; sheets, pipes, conduits for electrical installations, windows, doors and other profiles for the construction sector (ulterior fittings and external applications) as well as electrical and electronic parts such as switches, plugs and sockets, as well as bodywork and interior components for commercial vehicles, in particular for the automotive sector.
• domestic appliances such as televisions, juice extractors, coffee machines, mixers
• office machines such as monitors, flat screens, notebooks, printers, copiers
• sheets pipes, conduits for electrical installations, windows, doors and other profiles for the construction sector (ulterior fittings and external applications) as well as electrical and electronic parts such as switches, plugs and sockets, as well as bodywork and interior components for commercial vehicles, in particular for the automotive sector.
• the molding compositions according to the invention can in particular also be used, for example, in the production of the following molded bodies or moldings: interior fittings for railway vehicles, ships, aircraft, buses and other motor vehicles, casings for electrical devices containing small transformers, casings for devices for processing and transmitting information, casings and cladding for medical devices, massage devices and casings therefor, toy vehicles for children, prefabricated wall panels, casings for security devices and for televisions, heat-insulated transport containers, moldings for sanitary and bathroom fittings, gratings for ventilator openings and casings for gardening tools.
• the particulate crosslinked rubber base used for the preparation of component B was prepared by radical emulsion polymerization of butadiene in the presence of sodium salt of a specific TCD emulsifier as described in DE 3913509A1 (Example 1).
• the graft polymer dispersion is precipitated at 95° C. in a precipitation solution (consisting either of 2 parts magnesium sulfate and 100 parts water or of 2 parts magnesium sulfate, 1 part acetic acid and 100 parts water), filtered off and optionally (i.e., in the case of a comparison example) washed, and the resulting powder is dried at 70° C. in vacuo to a residual moisture content of ⁇ 0.5%.
• tert-butyl hydroperoxide dissolved in 5 parts by weight of water
• sodium ascorbate dissolved in 5 parts by weight of water
• the graft polymer dispersion is precipitated at 95° C. in a precipitation solution (consisting either of 2 parts magnesium sulfate and 100 parts water or of 2 parts magnesium sulfate, 1 part acetic acid and 100 parts water), filtered off and optionally (i.e. in the case of a comparison example) washed, and the resulting powder is dried at 70° C. in vacuo to a residual moisture content of ⁇ 0.5%.
• 2nd step emulsifier: 2.0 parts by weight of the potassium salt of stearic acid (Sigma-Aldrich).
• 2nd step emulsifier: 2.0 parts by weight of the potassium salt of stearic acid (Sigma-Aldrich).
• 2nd step emulsifier; 2.0 parts by weight of the potassium salt of stearic acid (Sigma-Aldrich).
• 2nd step emulsifier: 1.0 part by weight of the potassium salt of stearic acid (Sigma-Aldrich).
• 2nd step emulsifier: 2.0 parts by weight of the potassium salt of stearic acid (Sigma-Aldrich).
• emulsifier 3.0 parts by weight of the potassium salt of stearic acid (Sigma-Aldrich).
• 2nd step emulsifier: 2.0 parts by weight of the potassium salt of stearic acid (Sigma-Aldrich).
• 2nd step emulsifier: 2.0 parts by weight of the potassium salt of stearic acid (Sigma-Aldrich).
• 2nd step emulsifier: 2.0 parts by weight of the potassium salt of stearic acid (Sigma-Aldrich).
• 2nd step emulsifier: 2.0 parts by weight of the potassium salt of stearic acid (Sigma-Aldrich).
• 2nd step emulsifier; 2.0 parts by weight of the potassium salt of stearic acid (Sigma-Aldrich).
• 2nd step emulsifier; 2.0 parts by weight of the potassium salt of stearic acid (Sigma-Aldrich).
• 2nd step emulsifier: 2.0 parts by weight of the potassium salt of stearic acid (Sigma-Aldrich).
• Precipitation precipitation solution magnesium sulfate/water.
• the coagulum obtained after the precipitation is filtered off (about 20 liters of filtrate solution) and washed carefully (i.e. suspended 4 times in distilled water and then filtered off and washed with a large amount of distilled water (about 80 liters per 1 kg of polymer in total)).
• 2nd step emulsifier: 2.0 parts by weight of the potassium salt of stearic acid (Sigma-Aldrich).
• emulsifier graft polymerization was carried out with 1 part by weight of the sodium salt of a disproportionated resin acid emulsifier Dresinate 731 (Abieta-Chemie).
• 2nd step emulsifier; graft polymerization was carried out with 1 part by weight of the sodium salt of a disproportionated resin acid emulsifier Dresinate 731 (Abieta-Chemie).
• emulsifier graft polymerization was carried out with 2 parts by weight of the sodium salt of a disproportionated resin acid emulsifier Dresinate 731 (Abieta-Chemie).
• emulsifier 2.0 parts by weight of sodium dodecylsulfate (Sigma-Aldrich).
• emulsifier 2.0 parts by weight of sodium dodecylsulfate (Sigma-Aldrich).
• emulsifier 2.0 parts by weight of sodium dodecylsulfate (Sigma-Aldrich).
• emulsifier 2.0 parts by weight of sodium dodecylsulfate (Sigma-Aldrich).
• emulsifier 2.0 parts by weight of sodium dodecylsulfate (Sigma-Aldrich).
• emulsifier 2.0 parts by weight of sodium dodecylsulfate (Sigma-Aldrich).
• emulsifier 1.5 parts by weight of sodium dodecylsulfate (Sigma-Aldrich).
• 2nd step emulsifier: 1.5 parts by weight of Dowfax 2A1 (sodium salt(s) of a sulfonated diphenyl ether derivative) (Sigma-Aldrich).
• 2nd step emulsifier: 2.0 parts by weight of Dowfax 2A1 (sodium salt(s) of a sulfonated diphenyl ether derivative) (Sigma-Aldrich).
• emulsifier 1.0 part by weight of Dowfax 3B2 (sodium salt(s) of a sulfonated diphenyl ether derivative) (Sigma-Aldrich).
• emulsifier 1.0 part by weight of sodium dodecylsulfate (Sigma-Adrich).
• compositions listed in Tables 1 to 3 are prepared in a 1.5 liter internal kneader.
• YI yellowness index
• ⁇ ⁇ ⁇ MVR ⁇ ( hyrdr ) MVR ( after ⁇ ⁇ FWL ⁇ ⁇ storage - MVR ⁇ ( before ⁇ ⁇ storage ) MVR ⁇ ( before ⁇ ⁇ storage ) ⁇ 100 ⁇ %
• ⁇ ⁇ ⁇ MVR ⁇ ( proc . ) MVR ⁇ ( after ⁇ ⁇ storage ⁇ ⁇ ⁇ of ⁇ ⁇ the ⁇ ⁇ melt ) - MVR ⁇ ( before ⁇ ⁇ storage ) MVR ⁇ ( before ⁇ ⁇ storage ) ⁇ 100 ⁇ %
• compositions 2, 3 and 5 to 17 according to the invention exhibit a good inherent color with yellowness indices ⁇ 30, which were measured on the molded bodies injection molded at 260° C. If these compositions 2, 3 and 5 to 17 are compared with composition 18, in which component B16 was prepared in the absence of an emulsifier, the positive effect of the fatty acid emulsifier (potassium stearate) on the inherent color of the polycarbonate compositions is clear—the yellowness index measured for composition 18 is significantly higher at 33 (injection molding at 260/80° C.).
• compositions 2, 3, 5 to 17 are compared with compositions 24 to 36 known from the prior art, which according to EP-A 0 900 827 are substantially free of basic impurities and do not degrade polycarbonate, it is found that yellowness indices markedly greater than 30, with values of up to 56, are observed (injection molding at 260°/80° C.) in all the comparison compositions and that the hydrolytic and melt viscosity of the compositions from comparison examples are only at a good level when the emulsion graft component B was washed in the working-up step.
• Compositions 2, 3 and 5 to 17 according to the invention exhibit a markedly better inherent color than compositions 24 to 36 in all cases, comparably good hydrolytic stability and markedly better melt or processing stability in several cases.
• compositions 1 and 4 show that it is necessary either to work up the emulsion graft polymers of component B under acidic conditions (pH ⁇ 7) or to use acid-containing additives in the preparation of the polycarbonate molding compositions by melt compounding.
• compositions 2 and 4 exhibit a good inherent color with yellowness indices ⁇ 30 when injection molded at 260° C., they turn markedly brown at higher temperatures, so that YI of over 60 are determined when they are injection molded at 300° C.
• the hydrolytic stability and melt stability of compositions 2 and 4 are also significantly poorer than those of the compositions according to the invention, in which acidic working, up of the graft emulsion took place or acidic additives were added to the molding compositions.
• magnesium salts are used in the working up of the ABS emulsions according to component B, these magnesium salts bind to the carboxylate-containing emulsifiers; In the examples of this application, potassium stearate was used as emulsifier, so that magnesium stearate was formed during the precipitation. On the other hand, magnesium salts of saturated fatty acids are often used as lubricants in plastics processing. In comparison compositions 22 and 23, 0.4 part by weight of magnesium stearate was used in the melt compounding, which corresponds to an amount of magnesium stearate which is formed on coagulation of the graft-polymer dispersions of Examples B(1) to B(15). In composition 23, an acid was additionally used, which was to neutralize the basic constituents.
• composition 22 differs from all the compositions 2, 3, 5 to 17 according to the invention both by a poorer natural color and by extraordinarily poor hydrolytic stability and melt and processing stability.
• the neutralizing action of the acid used is shown in the case of comparison composition 23—the inherent color of this composition is not adversely affected and remains very light, at 28 ⁇ YI ⁇ 30, on injection molding both at 260° C. and at 300° C.
• the hydrolytic stability and melt or processing stability are very poor, however.
• compositions according to the invention which contain emulsifiers based on saturated fatty acids, exhibit, both a good inherent color and good hydrolytic stability and melt or processing stability, while the compositions in which magnesium salts of the saturated fatty acids were used as additive exhibit extraordinarily poor hydrolytic and melt or processing stability and, in some cases, a poor inherent, color.
• Table 6 summarizes the properties of the PC/ABS compositions containing flameproofing additives.
• the flameproofing additive D.1 contains acid groups (acid number of 0.06 mg/g of substance), so that the addition of additional acidic additives is not necessary.
• Comparison composition, 43 which contains a resin acid emulsifier in component B, exhibits a significantly poorer natural color at 300° C., with a yellowness index of 31, for a small amount of emulsion graft polymer.
• Magnesium stearate was added to comparison composition 44, with the result that its inherent color was improved but its hydrolytic stability was markedly impaired. The melt and processing stability remained at an excellent level.

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