MXPA00012943A - Flame resistant polycarbonate/abs plastic molding materials - Google Patents

Abstract

The invention relates to polycarbonate/ABS plastic molding materials furnished with phosphazenes which exhibit an excellent flame protection and very good processing properties, whereby the graft polymer is produced using a material polymerization, solvent polymerization, or material-suspension polymerization method.

Description

MOLDS OF MOLDING OF POLT CARBON ATO- ABS IGNÍFUGAS. FIELD OF THE INVENTION The present invention relates to polycarbonate-ABS molding compositions, finished with phosphazenes, which have excellent flame protection and very good processing properties, the graft polymer being prepared by means of bulk polymerization processes. , in solution or in mass-suspension. DESCRIPTION OF THE PRIOR ART DE-A-196 16 968 discloses polymerizable phosphazene derivatives, processes for their preparation and their use as hardenable binders for varnishes, coatings, fillers, masses for plastering, glues, castings or sheets. In WO 97/40 092, flame-protected molding compositions consisting of thermoplastic polymers and unsubstituted phosphazenes (type PNn.xH, .y) are described. EP-A-728 811 discloses a thermoplastic mixture consisting of aromatic polycarbonate, graft copolymer, copolymer and phosphazenes, which has good flame-protective properties, impact resistance and dimensional stability to heat. DETAILED DESCRIPTION OF THE INVENTION The task of the present invention is the provision of masses (ie polycarbonate / ABS molding with excellent flame resistance and excellent processing properties with good creep behavior and reduced deposit formation on the tools during the transformation process.) This spectrum of properties is especially required when Ref: 125451 apply in the field of data processing technology such as, for example, for monitor housings, printers, reproducers, copiers, etc. It has now been found that PC / ABS molding compositions containing phosphazenes and a graft polymer prepared by means of a Redox initiator system have the desired properties. The object of the invention are therefore thermoplastic molding compositions containing A) from 40 to 99, preferably from 60 to 98.5 parts by weight of aromatic polycarbonate and / or polyester carbonate, B) from 0.5 to 60, preferably from 1 to 40, especially from 2 to 25 parts by weight of graft polymer, prepared by mass polymerization, solution or mass-suspension methods of B. 1) 50 to 95, preferably 65 to 98% by weight of one or more vinyl monomers on B .2) to 1, preferably 35 to 2% by weight of one or more graft bases with a vitreous transition temperature < 10 ° C, preferably < 0 ° C, particularly preferably < -10 ° C, C) from 0 to 45, preferably from 0 to 30, particularly preferably from 2 to 25 parts by weight of at least one thermoplastic polymer, chosen from the group of vinyl (co) polymers and polyalkylene terephthalates, D) of 0 1 to 50, preferably 2 to 35, particularly preferably 5 to 25 parts by weight of at least one component, selected from the group of phosphazenes of the formulas where R are respectively the same or different and mean amino, alkyl having from 1 to 8 carbon atoms, respectively halogenated, optionally halogenated with fluorine, or means alkoxy with 1 to 8 carbon atoms, cycloalkyl with 5 to 6 carbon atoms, substituted respectively by alkyl, preferably by alkyl having 1 to 4 carbon atoms, and / or by halogen, preferably chlorine, bromine, aryl with 6 to 20 carbon atoms, preferably phenyl or naphthyl, aryloxy with 6 to 20 atoms carbon, preferably phenoxy, naphthyloxy or aralkyl with 7 to 12 carbon atoms, preferably phenyl-alkyl with 1 to 4 carbon atoms, means 0 or a number from 1 to 15, preferably means a number from 1 to 10, E) from 0 to 5 parts by weight, preferably from 0.1 to 1 part by weight, particularly preferably from 0.1 to 0.5 parts by weight of fluorinated polyolefin.

Component A. The aromatic polycarbonates and / or the aromatic polyester carbonates, suitable according to the invention, according to component A, are known from the literature or can be prepared according to 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 DE-AS 1 495 626, DE-OS 2 232 877, DE-OS 2 703 376, DE-OS 2 714 544, DE-OS 3 000 610 , DE-OS 3 832 396, for the preparation of aromatic polyester carbonates, for example DE-OS 3 077 934). The preparation of the aromatic polycarbonates is carried out, for example, by reaction of diphenols with carbonyl halides, preferably phosgene and / or aromatic dicarbonyl dihalides, preferably benzodicarbonyl dihalides, according to the cross-phase interface, optionally with use of chain switches, for example mono-phenols and optionally with trifunctional branching agents or with a functionality greater than 3, for example triphenols or tetraphenols. The diphenols for the preparation of the aromatic polycarbonates and / or the aromatic polyester carbonates are preferably those of the formula (III) wherein A means a single bond, alkylene with 1 to 5 carbon atoms, alkylidene with 2 to 5 carbon atoms, cycloalkylidene with 5 to 6 carbon atoms, -O-, -SO-, -CO-, -S -, -SO2-, arylene with 6 to 12 carbon atoms, on which other aromatic rings containing, if appropriate, heteroatoms, or a radical of formula (IV) or (V) may be condensed.

~ Q (x ') m (IV) R A R. " 13 respectively denotes alkyl having 1 to 12 carbon atoms, preferably methyl, halogen, preferably chlorine and / or bromine. x mean respectively, independently of each other, 0, 1 or 2, p means 1 or 0, and R7 and R8 which can be chosen individually for each X ', mean, independently of each other, hydrogen or alkyl having 1 to 6 carbon atoms, preferably hydrogen, methyl or ethyl, X1 signifies carbon and rn signify an integer from 4 to 7, preferably 4 or 5, with the proviso that at least one atom X1, R7 and R8 simultaneously mean alkyl. Preferred diphenols are hydroquinone, resorcin, dihydroxydi-phenols, bis- (hydroxyphenyl) -alkanes with 1 to 5 carbon atoms, bis- (hydroxyphenyl) -cycloalkanes with 5 to 6 carbon atoms, bis- (hydroxyphenyl) -ethers, bis- (hydroxyphenyl) -sulfoxides. bis- (hydroxyphenyl) -ketones, bis- (hydroxyphenyl) -sulfones and a, a-bis- (hydroxyl-phenyl) -diisopropyl-benzenes as well as their brominated derivatives in the nucleus and / or chlorinated in the nucleus. Particularly preferred diphenols are 4,4'-dihydroxydiphenyl, bisphenol-A, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 1, -bis- (4-hydroxyphenyl) -3.3.5-trimethylcyclohexane, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenyl-sulfone and its di- and tetrabrominated or chlorinated derivatives, 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. Particularly preferred is 2,2-bis- (4-hydroxyphenyl) -propane (bisphenol-A). The diphenols can be used individually or as arbitrary mixtures. Diphenols are known from the literature or can be obtained according to methods known from the literature. Suitable chain terminators for the preparation of the aromatic, thermoplastic polycarbonates are, for example, phenol, p-chlorophenol, p-tert.-butylphenol or 2,4,6-tribromophenol, as well as long-chain alkyl phenols, such as such as 4- (1, 3-tetramethylbutyl) -phenol according to DE-OS 2 842 005 or mono-alkylphenol or dialkylphenols with a total of 8 to 20 carbon atoms in the alkyl substituents, such as 3-5. -di-tert-butylphenol, p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol and 2- (3,5-dimethylheptyl) -phenol and 4- (3, 5-dimethylheptyl) -phenol. The amount of chain switches to be used is generally between 0.5% by mole and 10% by mole based on the sum in moles of the diphenols used in each case. The aromatic polycarbonates, thermoplastics, have weight-average molecular weights (Mw, measured for example by ultracentrifugation or by measurement of light scattering) of 10,000 to 200,000, preferably 20,000 to 80,000. The aromatic, thermoplastic polycarbonates can be branched in a known manner and in particular preferably by the incorporation of 0.05 to 2.0 mole%, based on the sum of the diphenols used, of trifunctional compounds or with a functionality greater than 3. , for example those with three or more phenolic groups. Both homopolycarbonates and copolycarbonates are suitable. For the preparation of the copolycarbonates according to the invention 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 polydiorganosiloxanes. with terminal hydroxy-aryloxy groups. These are known (see for example US Pat. No. 3 419 634) or can be prepared according to methods known from the literature. The preparation of the copolycarbonates containing polydiorganosiloxane is described, for example, in DE-OS 3 334 782. Preferred polycarbonates are, in addition to the homopolycarbonates of bisphenol-A, the copolycarbonates of bisphenol-A with up to 15 mol% , referred to the sum in moles of diphenols, of other diphenols mentioned as preferred or cited, especially preferred, especially 2-2-bis (3,5-dibromo-4-hydroxyphenyl) -propane. The aromatic dicarbonyl dihalogenides for the preparation of the aromatic polyester carbonates are preferably the diacid dichlorides of isophthalic acid, terephthalic acid, diphenylether-4,4'-dicarboxylic acid and naphthalene-2,6-dicarboxylic acid. Mixtures of the diacid dichlorides of isophthalic acid and terephthalic acid in the ratio between 1: 20 and 20: 1 are particularly preferred. In the preparation of polyester carbonates, a halide of carbonic acid, preferably phosgene in the same way, is also used concomitantly. of bifunctional acid derivative. As chain terminators for the preparation of the aromatic polyestercarbonates, in addition to the aforementioned monophenols, also their chlorocarbonic acid esters as well as the acyl chlorides of aromatic monocarboxylic acids, which may be substituted by groups, may be used. alkyl with 1 to 22 carbon atoms or halogen atoms, as well as chlorides of aliphatic monocarboxylic acids with 2 to 22 carbon atoms. The quantity in chain switches amounts, respectively, of 0, 1 to 10 mol%, referred in the case of the phenolic chain terminators to the moles of diphenols and in the case of the monocarboxylic acid chloride chain terminators to the moles of the dicarboxylic acid dichlorides. The aromatic polyester carbonates may also contain incorporated aromatic hydroxycarboxylic acids. The aromatic polyester carbonates can be both linear and branched in a known manner (see also DE-OS 2 940 024 and DE-OS 3 007 934). Branching agents which can be used are, for example, trifunctional carboxylic acid chlorides or with a functionality greater than 3, such as trimesin 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 0.01 to 1.0% in moles, (based on the chlorides of the dicarboxylic acids used) or trifunctional phenols or with a functionality greater than 3, such as fluoroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) -heptene-2,4,4-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) -phenyl-methane, 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'-dihydroxytriphenyl] -methyl] -benzene, in amounts of 0.01 to 1.0 mol% based on the diphenols used. The branched phenolic agents can be arranged with the diphenols, the branching agents of acyl chloride can be incorporated together with the acyl dichlorides. In aromatic polyester carbonates, thermoplastics, the proportion in carbonate structural units can vary arbitrarily. Preferably, the proportion of carbonate groups is up to 100 mol%, especially up to 80 mol%, more preferably up to 50 mol%, based on the sum of the ester groups and the carbonate groups. Both the ester ratio and also the carbonate content of the aromatic polyester carbonates can be present in the polycondensate both in block form or in a statistical manner. The relative solution viscosity (? Re) of the aromatic polycarbonates and the polyester carbonates is in the range from 1.18 to 1.4, preferably from 1.22 to 1.3 (measured in solutions of 0.5 g. of polycarbonate or polyester carbonate in 100 ml of methylene chloride solution at 25 ° C). The aromatic carbonates, thermoplastics and the polyestercarbonates can be used alone or in arbitrary mixtures with each other. Component B. Graft polymer B, modified with rubber, comprises a statistical (co) polymer consisting of monomers B.l. l and B. l .2, as well as a B.2 rubber grafted with the (co) statistical polymer constituted by B.l. and B, 1, 2, the obtaining of B being verified in a known manner according to a mass or solution or mass-suspension polymerization process, as described, for example, in US Pat. No. 3,243,481, US Pat. No. 3,509,237, US 3 660 535, 4 221 833 and US 4 239 863. Examples of monomers B. l. They are styrene, -methylstyrene, styrenes substituted in the nucleus by halogen or by alkyl, such as p-methylstyrene, p-chlorostyrene, alkyl (meth) acrylate with 1 to 8 carbon atoms such as methyl methacrylate, -butyl and t-butyl acrylate. Examples of monomers B. l.2 are unsaturated nitriles such as acrylonitrile, methacrylonitrile, C 1 -C 8 alkyl (meth) acrylate such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate, derivatives ( such as anhydrides and imides) of unsaturated carboxylic acids such as maleic anhydride and N-phenyl-maleimide or mixtures thereof. The preferred monomers B.l.l. are styrene, methylstyrene and / or methyl methacrylate, the preferred monomers B.l.2 are acrylonitrile, maleic anhydride and / or methyl methacrylate.

Particularly preferred monomers B.l. They are styrene and B. 1,2 acrylonitrile. Suitable rubbers B.2 suitable for graft polymers B, modified with rubber, are, for example, diene rubbers, EP (D) M rubbers, ie those based on ethylene / propylene and, if appropriate, acrylate rubbers, of polyurethane, silicone, chloroprene and ethylene / vinyl acetate. Preferred rubbers B.2 are diene rubbers (for example based on butadiene, isoprene, etc.) or mixtures of diene rubbers or copolymers of diene rubbers or their mixtures with other copolymerizable monomers (for example according to B. l and B. 1.2), with the proviso that the vitreous transition temperature of component B.2 is below 10 ° C, preferably below -10 ° C. A pure polybutadiene rubber will be especially preferred. Component B may contain, if necessary and when, for this reason, the rubber properties of component B.2 are not negatively influenced, additionally in addition small amounts, usually less than 5% by weight, preferably less than 2% by weight. % by weight, based on B.2, of ethylenically unsaturated monomers with a crosslinking action. Examples of such crosslinking monomers are di- (meth) acrylenediol acrylate, polyester di- (meth) acrylate, divinylbenzene, trivinylbenzene, triallyl cyanurate, allyl (meth) acrylate, diallyl maleate and ferrous fumarate. diallyl. The graft polymer B, modified with rubber, is obtained by graft polymerization from 50 to 99, preferably from 65 to 98, particularly preferably from 75 to 97 parts by weight of a mixture consisting of 50 to 99, preferably 60 to 95 parts by weight of monomers according to B. l. and 1 to 50, preferably 5 to 40 parts by weight of monomers according to B. 1 .2 in the presence of 1 to 50, preferably from 2 to 35, particularly preferably from 2 to 15, in particular from 2 to 13, by weight of the rubber component B.2, the graft polymerization being carried out according to a bulk or solution or mass-suspension polymerization process. The main thing in obtaining the B-grafted polymers, modified with rubber, is that the rubber component B.2 is present, before the graft polymerization in dissolved form in the mixture of the monomers B. l. l and B. l.2. The rubber component B.2 therefore must not be so strongly cross-linked that a dissolution in B. l is impossible. l and B. l .2, nor should B.2 be presented at the beginning of the graft polymerization already in the form of discrete particles. The morphology of the particles important for the properties of the product of B and the increasing crosslinking of B.2 are formed only during the course of graft polymerization (see, for example, Ullmann, Encyclopaedia der technischen Chemie, volume 19, pages 284 and following 4th edition 1980). The statistical copolymer constituted by B. l. and B.1.2 is usually present in polymer B, on the one hand over-grafted or incorporated by grafting on rubber B.2, this mixed graft polymer formed discrete particles in polymer B. The part of the copolymer over-grafted or incorporated by graft constituted by Bl. and Bl.sub.2 on the whole of the copolymer formed by B. 1. and Bl.sub.2 - that is to say the yield in graft (= proportion by weight of the graft monomers actually grafted with respect to the graft monomers. used in total x 100, data in%) - it should be in this case from 2 to 40%, preferably from 3 to 30%, particularly preferably from 4 to 20%. The average diameter of the particles of the resulting grafted rubber particles (determined by counting in photography by electron microscopy) is in the range of 0.5 to 5 μm, preferably 0.8 to 2.5 μm. Component C. Component C comprises one or more C.l thermoplastic vinyl (co) polymers and polyalkylene terephthalate C.2. C.sub.1 vinyl polymers are suitable polymers of at least one monomer from the group consisting of vinylaromatics, vinylcyanides (unsaturated nitriles), esters of alkyl (with 1 to 8 carbon atoms) of methacrylic acid, unsaturated carboxylic acids as well as derivatives, (such as anhydrides and imides) of unsaturated carboxylic acids. Particularly suitable are (co) polymers consisting of C.l.l. 50 to 99, preferably 60 to 80, parts by weight of vinyllacromatoses and / or vinylaromatos substituted in the nucleus such as for example styrene, α-methylstyrene, p-methylstyrene , p-chlorostyrene and / or alkyl esters (with 1 to 4 carbon atoms) of methacrylic acid, such as, for example, methyl methacrylate, ethyl methacrylate) and C. 1 .2 l to 50, preferably 20 to 40 parts by weight of vinyl cyanides (unsaturated nitriles) such as acrylonitrile and methacrylonitrile and / or esters of alkyl (1 to 8 carbon atoms) of the acid (meth) acrylic (such as for example 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) of unsaturated carboxylic acids (e.g. maleic acid anhydride and N-phenyl-maleinimide).

The (co) polymers C.l are resinous, thermoplastic and rubber-free. Particularly preferably, the copolymer consists of C. l .l styrene and C.l.2 acrylomethyl. The (co) polymers according to C.l are known and can be prepared by radical polymerization, especially by emulsion, suspension, solution or bulk polymerization. The (co) polymers according to component C.l preferably have molecular weights M w (weight average, determined by light scattering or by sedimentation) between 15,000 and 200,000. The polyalkylene terephthalates of component C.2 are reaction products of aromatic dicarboxylic acids or their reactive derivatives, such as dimethyl esters or anhydrides, and aliphatic, cycloaliphatic or araliphatic diols as well as 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 components of terephthalic acid moieties and at least 80% by weight, preferably at least 90% by mole, referred to the diol components of ethylene glycol residues and / or butanediol-1,4 residues. Preferred polyalkylene terephthalates can contain, in addition to residues of terephthalic acid, up to 20% by mole, preferably up to 10% by mole, of residues of other aromatic or cycloaliphatic dicarboxylic acids with 8 to 14 carbon atoms or of aromatic dicarboxylic acids or cycloaliphatics with 8 to 14 carbon atoms or aliphatic dicarboxylic acids with 4 to 12 carbon atoms, such as, for example, phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4-acid residues, 4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexane-diacetic acid. Preferred polyalkylene terephthalates can contain, in addition to ethylene glycol or butanediol-1,4 residues, up to 20% by mole, preferably up to 10% by mole, of other aliphatic diols with 3 to 12 carbon atoms or cycloaliphatic diols with 6 to 12 carbon atoms. to 21 carbon atoms, for example, 1,3-propanediol, 2-ethyl-propanediol-1,3, neopentyl glycol, pentanediol-1,5, hexanediol-1,6,6-cyclohexane-dimethanol-1,4 residues. , of 3-ethylpentanediol-2,4, of 2-methylpentanediol-2,4, of 2,2,4-trimethyl-pentanediol-1,3, of 2-ethylhexanediol-1,3, of 2,2-diethylpropanediol- l, 3, of hexanediol-2,5, of l, 4-di- (β-hydroxyethoxy) -benzene, of 2,2-bis- (4-hydroxycyclohexyl) -propane, of 2,4-dihydroxy-1, 1, 3, 3-tetramethyl-cyclobutane, 2,2-bis- (4-β-hydroxyethoxy-phenyl) -propane and 2,2-bis- (4-hydroxy-propoxyphenyl) -propane (DE- OS 2 407 674, 2 407 776, 2 715 932). The polyalkylene terephthalates can be branched by incorporating relatively small amounts of tri or tetravalent alcohols or tri or tetrabasic carboxylic acids, for example according to DE-OS 1 900 270 and US Pat. No. 3,692,744. Preferred examples of branching agents are trimesinic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol. Especially preferred are polyalkylene terephthalates which have been prepared only from terephthalic acid and its reactive derivatives (for example its dialkyl esters) and ethylene glycol and / or butanediol-1,4, and mixtures of these polyalkylene terephthalates. Mixtures of the polyalkylene terephthalates contain from 1 to 50% by weight, preferably from 1 to 30% by weight, of polyethylene terephthalate and from 50 to 99% by weight, preferably from 70 to 99% by weight, of polybutylene terephthalate. The polyalkylene terephthalates which are preferably used have, in general, a limit viscosity of 0.4 to 1.5 dl / g, preferably 0.5 to 1.2 dl / g, measured in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C in the Ubbelohde viscometer. The polyalkylene terephthalates can be prepared according to known methods (see for example Kunststoff-Handbuch, Volume VIII, page 695 et seq., Carl-Hanser-Verlag, München 1973). Component D. The phosphazenes according to component D, which are used according to the present invention, are linear phosphazenes according to formula (la) or cyclic phosphazenes according to formula (Ib). where R and k have the meaning indicated above. Examples which may be mentioned are: propoxyphosphazene, phenoxyphosphazene, methyl phenoxyphosphazene, aminophosphazene and fluoroalkylphosphazene.

Phenoxyphosphazene is preferred. The phosphazenes can be used alone or in the form of mixtures. The rest R can always be the same or 2 or several residues of the formulas (la) and (Ib) can be different. Phosphazenes and their preparation have been described, for example, in EP-A-728 811, DE-A-1 961 668 and WO 97/40 092. Component E. Fluorinated polyolefins E are of high molecular weight and have transition temperatures vitreous above -30 ° C, generally above 100 ° C, contained in fluorine, preferably from 65 to 76, especially from 70 to 76% by weight, average diameter of the d50 particles from 0.05 to 1,000 , preferably from 0.08 to 20 m. In general, the fluorinated polyolefins E have a density of 1.2 to 2.3 g / cm3. The preferred fluorinated polyolefins E are polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene copolymers (hexafluoro-propylene and ethylene / tetrafluoroethylene) The fluorinated polyolefins are known (see the publications "Vinyl and Related Polymers" by Schildknecht, John Wiley & Sons, Inc., New York, 1962, pages 484-494; "Fluorpolymers" of Wall, Wiley-Interscience, John Wiley & Sons, Inc., New York, Volume 13, 1970, pages 623-654; "Modern Plastics Encyclopedia", 1970-1971, volume 47, No. 10 A, October 1970, Me Graw-Hill, Inc., New York, pages 134 and 774; "Modern Plastic Encyclopedia ", 1975-1976, October 1975, volume 52, No. 10 A. Me Graw-Hill, Inc., New York, pages 27, 28 and 472 and US-PS 3 671 487, 3 723 373 and 3 838 092). These can be prepared according to known processes, for example by polymerization of tetrafluoroethylene in aqueous medium with a catalyst that forms free radicals, for example sodium, potassium or ammonium peroxydisulfate, at pressures of 7 to 71 kg / cm2 and at temperatures of 100 to 200 ° C, preferably at temperatures of 20 to 100 ° C. (For more details, see US Pat. No. 2 393 967). Depending on the application form, the density of these materials can be between 1.2 and 2.3 g / cm3, the average particle size between 0.5 and 1,000 m. The preferred fluorinated polyolefins E according to the invention are tetrafluoroethylene polymers with an average particle diameter of 0.05 to m, preferably 0.08 to 10 m, and a density of 1.2 to 1.9 g / ci and are preferably used in the form of a coagulated mixture of emulsions of tetrafluoroethylene E polymers with emulsions of a graft polymer . Suitable fluorinated polyolefins E, used in powder form, are tetrafluoroethylene polymers with an average particle diameter of 100 to 1,000 m and densities of 2.0 g / cm 3 to 2.3 g / cm 3. In order to obtain a coagulated mixture consisting of a graft copolymer B and the component E, an aqueous emulsion (latex) of a graft polymer B is first mixed with a finely divided emulsion of a tetrafluoroethylene polymer E; Suitable tetrafluoroethylene polymer emulsions usually have a solids content of 30 to 70% by weight, in particular 50 to 60% by weight, preferably 30 to 35% by weight. In the emulsion mixture the equilibrium ratio between the graft polymer and the tetrafluoroethylene polymer E is from 95: 5 to 60:40. The emulsion mixture is then coagulated in a known manner, for example by spray drying, lyophilization or coagulation by means of the addition of salts, acids, inorganic or organic bases or organic solvents miscible with water, such as alcohols, ketones, preferably at temperatures of 20 to 50 ° C, especially 50 to 100 ° C. If necessary, it can be dried at 50 to 200 ° C, preferably at 70 to 100 ° C. Suitable emulsions of tetrafluoroethylene polymer are commercially available products and are offered, for example, by the DuPont Company as Teflon® 30N. The molding compositions according to the invention can contain at least one of the usual additives, such as lubricants, mold release agents, nucleating agents, antistatics, stabilizers as well as dyes and pigments. The molding compositions according to the invention can contain up to 35 % by weight, based on the whole of the molding composition, of another flame protection agent, which acts synergistically if necessary. Examples of other flame retardants, halogenated organic compounds such as decabromobisphenyl ether, tetrabromobisphenol, halogenated inorganic compounds such as ammonium bromide, nitrogenous compounds, such as melamine, melamine formaldehyde resins, hydroxy compounds, can be cited as other flame retardants. inorganics such as Mg hydroxide, Al, inorganic compounds such as antimony oxides, barium metaborate, hydroxyantimonate, zirconium oxide, zirconium hydroxide, molybdenum oxide, ammonium molybdate, zinc borate, ammonium borate, metaborate barium, talc, silicate, silicon dioxide and tin oxide as well as siloxane compounds. The molding compositions according to the invention containing components A to E and, if appropriate, other known additives such as stabilizers, dyes, pigments, lubricants and mold release agents, nucleating agents as well as antistatics, are prepared by mixing, in a known manner, of the corresponding components and formation of melt blends and extrusion of the melt at temperatures of 200 ° C to 300 ° C in conventional devices such as internal kneaders, extruders and double-shaft spindles, the component E being preferably used in the form of coagulated mixture already mentioned. The mixing of the individual components can be carried out in a known manner both successively and simultaneously, and specifically at about 20 ° C (room temperature) as well as at a higher temperature. Thus, it is also an object of the present invention a method for obtaining molding compositions. The thermoplastic molding compositions according to the invention are suitable, owing to their excellent flame resistance and good mechanical properties, for the production of moldings of any kind, especially those with high demands on processing performance. These include complicated shaped parts with several casting points and parts for thin-walled housings with wall thicknesses < 2 mm, preferably < 1, 5 mm. The molding compositions of the present invention can be used for the production of moldings of any type. In particular, moldings can be produced by injection molding. Examples of moldable bodies that can be manufactured are: parts for housings of any kind, for example for household appliances such as juicing apparatus, coffee machines, blenders, for office machines such as monitors, printers, copiers, or plates coverage for the construction sector and parts for the automotive sector. They can also be used in the electronics sector, since they have very good electrical properties. Another form of the elaboration consists of the manufacture of bodies molded by deep drawing from plates or sheets manufactured previously. Another object of the present invention is therefore the use of the molding compositions according to the invention for the production of moldings of any kind, preferably those mentioned above, as well as the moldings formed by the molding compositions according to the invention. Furthermore, the molding compositions according to the invention can be used, for example, for the production of molded bodies or the following molded parts: Interior components for railway vehicles (FR). Hubcaps Carcasses of electrical appliances that contain small transformers. Carcasses for devices for the distribution and transmission of information.

Carcasses and coating for medicinal purposes. Massage devices and housings for them. Toy vehicles for children. Flat elements for walls. Enclosures for security devices. Rear bumper. Thermally insulated transport containers. Device for the maintenance or care of small animals. Molded parts for sanitary and bathroom equipment.

Cover grilles for ventilation openings. Molded parts for garden sheds and tools. Carcasses for gardening devices. Examples Component A. Linear polycarbonate based on bisphenol A with a relative solution viscosity of 1.26, measured in CH2C12 as solvent at 25 ° C and at a concentration of 0.5 g / 100 ml. Component B. B. l ABS mass polymer from DOW Chemical Companys Midland, Michigan USA (trade name Magnum 3304). Acrylonitrile: butadiene: styrene = 22.0: 10.2: 67.8. B.2 Comparative. Graft polymer of 40 parts by weight of a copolymer of styrene and acrylonitrile in the proportion of 73:27 on 60 parts by weight of crosslinked polybutadiene rubber in the form of particles (mean particle diameter d50 = 0.28 m), prepared by emulsion polymerization.

Styrene / acrylonitrile copolymer with a weight ratio of styrene / acrylonitrile of 72:28 and a limit viscosity of 0.55 dl / g (measured in dimethylformamide at 20 ° C). (Component D. Phenoxyphosphazene of the formula Commercial product: P-3800, Nippon Soda Co., Ltd. Japan. Pentaerythritol tetrastearate is used as the release agent. Component E. Tetrafluoroethylene polymer as a coagulated mixture constituted by an emulsion of graft polymer SAN (graft polymer of 40 parts by weight of a copolymer constituted by styrene and acrylonitrile in the proportion of 73:27 on 60 parts by weight of rubber of polybutadiene crosslinked in the form of particles, prepared by emulsion polymerization, mean particle diameter d50 = 0.28 m) in water and a tetrafluoroethylene polymer emulsion in water. The weight ratio between graft polymer B and the tetrafluoroethylene polymer E in the mixture is 90% by weight with respect to 10% by weight. The tetrafluoroethylene polymer emulsion has a solids content of 60% by weight, the average diameter of the particles is between 0.05 and 0.5 m. The graft polymer emulsion SAN has a solids content of 34% by weight and an average diameter of the latex particles of d50 = 0.28 m. Obtaining E. The emulsion of the tetrafluoroethylene polymer (Teflon 30 N of the DuPont Firm) is mixed with the emulsion of the graft polymer SAN B and stabilized with 1.8% by weight, based on the solid matter of the polymer, of phenolic an-antioxidant. The mixture is coagulated at 85 to 95 ° C with an aqueous solution of MgSO4 (bitter salt) and acetic acid at pH 4 to 5, filtered and washed to virtually no electrolyte, then released by centrifugation of the main quantity of water and then dried at 100 ° C to give a powder. This powder can then be transformed into masterbatch with the other components in the described devices. Fabrication and testing of the molding compositions according to the invention. The mixing of the components is carried out in an internal 3-liter kneader. The molded bodies are manufactured in an injection casting machine of the Arburg 270 E type at 260 ° C. The determination of the dimensional stability to heat according to Vicat B is carried out according to DIN 53 460 (ISO 306) in rods with dimensions of 80 x. 10 x 4 mm. The stress fracture behavior (ESC behavior) was tested on rods with dimensions of 80 x 10 x 4 mm, processing temperature 260 ° C. A mixture consisting of 60% by volume of toluene and 40% by volume of isopropanol was used as the test medium. The specimens were predilated by means of a circular arc template (previous dilation in percent) and stored at room temperature in the test medium. The stress fracture behavior was evaluated by the formation of cracks or rupture as a function of the previous dilation in the test medium. As a measure of deposit formation on the tools, thermogravimetric analysis (TGA) was used. In this case, the mass loss of the mixtures under N2 was determined as an inert gas in the temperature range from 0 to 400 ° C with a heating rate of 10 K / minute. For the evaluation, the mass loss at a temperature of 280 ° C corresponding to the usual processing temperature was used. The higher the numerical value, the greater the tendency towards the formation of deposits during the elaboration process. Low values show a small tendency to deposit formation. Table: Molding masses and their properties (Data in parts by weight) The molding compositions according to the invention are characterized by a favorable combination of flame protection properties and mechanical properties. It has also been found, surprisingly, that molding compositions containing mass ABS have additional advantages in the field of processing behavior. Both the creep behavior (MVR) and the loss of mass, which could be considered as a measure of the deposit formation on the tools, which is presented under the processing conditions, are clearly more favorable (approximately 20%) than in the case of molding compositions with ABS by emulsion. It is noted that in relation to this date, the best method known to the applicant, to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (10)

1. with 1 to 8 carbon atoms respectively halogenated, preferably halogenated with fluorine, or means alkoxy with 1 to 8 carbon atoms, cycloalkyl with 5 to 6 carbon atoms, optionally substituted by alkyl, preferably by alkyl with 1 to 4 carbon atoms, and / or by halogen, preferably chlorine, bromine, aryl with 6 to 20 carbon atoms, preferably phenyl or naphthyl, aryloxy with 6 to 20 carbon atoms, preferably phenoxy, naphthyloxy or aralkyl with 7 a 12 carbon atoms, preferably phenyl-alkyl with 1 to 4 carbon atoms, k means 0 or a number from 1 to 15, preferably means a number from 1 to 10, E) from 0 to 5 parts by weight of fluorinated polyolefin.
2. 2. - Samples of molding sagín la reiviiiiLcacd 1, characterized caraua amH ** i »of 60 to 98.5 parts by weight of A, from 1 to 40 parts by weight of B, from 0 to 30 parts by weight of C, of 2 up to 35 parts by weight of D, and from 0.1 to 1 part by weight of E.
3. 3. - Irolishing masses according to claims 1 and 2, characterized by -je sxit rHi of 2 haeta 25 parts by weight e c.
4. 4.- Molding masses according to claims 1 to 3, characterized porhe ccntiai? n from 5 to 25 parts of weight D.
5. 5.- Molding masses according to the preceding claims, being the Penelope palisates B.l pezplas face? Erizaaas because acptU? n = n. B. l. styrene, α-methylstyrene, styrenes substituted in the nucleus by halogen or by alkyl and / or alkyl (meth) acrylates with 1 to 8 carbon atoms and B. l.2 unsaturated nitriles, alkyl (meth) acrylates with 1 to 8 carbon atoms and / or unsaturated derivatives of carboxylic acids.
6. 6. Molding masses according to the preceding claims, the base for the graft being chosen at least between a rubber of the group of diene rubbers, rubbers EP (D) M, acrylate rubber, polyurethane, silicone, chloroprene and ethylene / vinyl acetate.
7. 7, -Molding-shaped according to the reivirdicaaa ^ ???? e contain at least one additive selected from the group consisting of lubricants and mold release agents, nucleating agents, antistatics, stabilizers, dyes and pigments.
8. 8. - molding masses s? Gjn the previous re? Vi? Icimà © s, cararteriza3 raiar contain other agents protective against the flame, which are different from component D.
9. 9. - Procedure for obtaining molding masses according to claim 1, c * -characterized par ^ they are mixed and transformed into mother mixtures by fusion.
10. 10. Use of the molding compositions according to claim 1, for obtaining molded bodies. 11.- Molded bodies, characterized by the manufacture from the beginning the molding compositions according to reivirdicators 1 to 8