MXPA00011970A - Flame-resistant polycarbonate abs moulding materials - Google Patents

Abstract

The present invention relates to thermoplastic polycarbonate moulding materials containing phosphazenes and special graft polymers that are produced by means of redox initiator systems. The inventive moulding materials are characterized by substantially improved mechanical properties.

Description

MOLDED ABS / POLYCARBONATE RESISTANT FLAME COMPOSITIONS Field of Invention The present invention relates to molded compositions of thermoplastic polycarbonate containing phosphazenes and special grafted polymers produced by means of initiating oxidation reduction systems and distinguished by their substantially improved mechanical properties.

Background of the Invention DE-A 196 16 968 describes polymerizable phosphazene derivatives, a process for the production thereof and the use thereof as curable binders for lacquered, coated, filled or surface compositions, adhesives, moils or films.

WO 97/40 092 describes flame-resistant molding compositions prepared from Ref. 1255354 of thermoplastic polymers and unsubstituted phosphazenes of the PNn_xH? -y type.

EP-A 728 811 discloses a thermoplastic linkage consisting of aromatic polycarbonate, graft copolymer, copolymer and phosphazenes which exhibit good flame-resistant properties, impact strength and heat resistance.

Neither EO 97/40 092 nor EP-A 728 811 describe a combination of phosphazenes and the special graft polymers.

EP-A-315 868 (= a US-A-7, 937, 285) describes molding compositions made from thermoplastic polycarbonates containing reducing oxidation graft polymers. There is no mention of adding phosphazenes.

Description of the invention The object of the present invention is to provide flame-resistant ABS / polycarbonate molding compositions which have very good mechanical properties such as nicked impact force, tensile stress resistance, flame resistance and resistance in the welding line . This range of properties is required in particular for applications in data processing, such as, for example, thin-walled covers for monitors, printers etc.

It has now been found that PC / ABS molding compositions containing phosphazenes and a graft polymer produced by means of a reduction oxidation initiator system exhibit the desired properties.

The present invention, accordingly, provides thermoplastic molding compositions containing: A) from 40 to 99, preferably from 60 to 98.5 parts by weight of an aromatic polycarbonate and / or polyester carbonate; B) from 0.5 to 60, preferably from 1 to 40, in particular from 2 to 25, parts by weight of a graft polymer, characterized in that the graft polymers B comprise: B.l) from 5 to 95, preferably from 30 to 80% by weight of one or more vinyl monomers and; B.2) from 95 to 5, preferably from 20 to 70% by weight of one or more particular dienes having a glass transition temperature of < 10 ° C, preferably from < 0 ° C, particularly preferably from < -20 ° C, which are produced by the emulsion polymerization, wherein the graft polymerization is carried out using an initiator system comprising an organic hydroperoxide and ascorbic acid, C) from 0 to 30, particularly preferably from 2 to 25 parts by weight of at least one thermoplastic polymer selected from the group comprising vinyl (co) polymers and polyalkylene terephthalates, D) from 0.1 to 50, preferably from 2 to 35, in particular from 5 to 25 parts by weight of at least one compound selected from the group comprising phosphazenes of the formulas which ones R is in each case identical or different and denotes amino, Ci to C8 alkyl, in each case optionally halogenated, preferably halogenated with fluorine, or Ci alkoxy up to C8, C5 cycloalkyl up to Ce, C6 aryl up to C2Q, preferably phenyl or naphthyl, aryloxy C up to C20, preferably phenoxy, naphthyloxy, or C7 aralkyl to Ci2, preferably phenyl-C? -C4 alkyl, in each case optionally substituted by alkyl, preferably C? -C4 alkyl, and / or halogen, preferably chlorine and / or bromine, k denotes 0 or a number from 1 to 15, preferably a number from 1 to 10, E) from 0 to 5, preferably from 0.1 to 1, particularly preferably from 0.1 to 0.5 parts by weight of fluorinated polyolefin.

Component A The aromatic polycarbonates and / or aromatic polyester carbonates of Component A which are suitable according to the invention are known from the literature or can be produced using processes known from the literature (reference, in relation to the production of aromatic polycarbonates, for example Schnell, Chemi s try &Physi cs of Polyca rbona tes, Interscience Publishers, 1964 and 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; with regard to the production of polyester carbonates, for example DE-OS 3 077 934).

The aromatic polycarbonates are produced, for example, by reacting diphenols with carbonic acid halides, preferably phosgene, and / or aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalides, by the process of the interface phase, optionally using chain, for example monophenols, and optionally using trifunctional or greater branched agents than trifunctional ones, for example triphenols or tetraphenols.

The diphenols for the production of aromatic polycarbonates and / or aromatic polyester carbonates are preferably those of the formula (II) (H), where A means a single bond, C1-C5 alkylene, C2-Cs alkylidene, Cs-C6 cycloalkylidene, -O-, -SO-, -CO-, -S-, -S02-, C6-C12 arylene, in which additional aromatic rings optionally contain heteroatoms which can be melted, a residue of the formula (III) (IV) CH, B in each case means C? -C? 2 alkyl, preferably methyl, halogen, preferably chlorine and / or bromine x in each case mutually independently means 0, 1 or 2, p means 1 or 0, and R5 and R6 individually selectively, mutually independently of each X1, mean hydrogen or Ci-Cß alkyl. preferably hydrogen, methyl or ethyl, X1 means carbon, and m means an integer from 4 to 7, preferably 4 or 5, with the proviso that R5 and R6 are simultaneously alkyl in at least one atom of X1.

Preferred diphenols are hydroquinones, resorcinols, dihydroxydiphenols, bis (hydroxyphenyl) -alkanes-C-C5, bis- (hydroxyphenyl) -cycloalkanes-C5-C6, bis- (hydroxyphenyl) ethers, bis- (hydroxyphenyl) sulfoxides, bis- (hydroxyphenyl) ketones, bis- (hydroxyphenyl) sulfones and, a-bis- (hydroxyphenyl) diisopropylbenzenes together with the bromine ring and / or the chlorine ring derived therefrom.

Particularly preferred diphenols are 4,4'-dihydroxydiphenyl, bisphenol A, 2,4-bis- (4-hydroxyphenyl) -2-methylobutane, 1,1-bis- (4-hydroxyphenyl) cyclohexane, 1, 1 - bis (-hydroxy phenyl) -3,3,3-t-rimethylcyclohexane, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone together with the di- and tetrabromide or chloride 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- -hydroxyphenyl) propane. 2, 2-bis- (4-hydroxyphenyl) propane (bisphenol A) is particularly preferred.

The diphenols can be used individually or as any desired mixtures.

Diphenols are known from the literature or are obtained using processes known from the literature.

Chain terminators suitable for the production of the aromatic polycarbonates, ie, plastic-plastics, are, for example, phenol, p-chlorophenol, p-tert. -butylphenol or 2,4,6-tribromophenol, as well as long-chain alkylphenols, such as 4 - (1,3-tetmethylbutyl) -phenol according to DE-OS 2 842 005, or monoalkylphenols having a total from 8 to 20 carbon atoms in the alkyl substituents, such as 3,5-di-tert. -butylphenol, p-iso-octylphenol, p-tert. -oct ilphenol, p-dodecylphenol and 2- (3,5-dimethyheptyl) -phenol and 4- (3,5-dimethylheptyl) phenol. The amount of chain terminators used is generally between 0.5 mol% and 10 mol%, relative to the sum of moles of the diphenols used in each case.

The polycarbonates, thermoplastics, have weight average molecular weights (Mw, measured for example by ultracentrifugation or light scattering) of 10,000 to 200,000, preferably 20,000 to 80,000.

The aromatic polycarbonates, thermoplastics, can be branched in a known manner, preferably incorporating 0.05 to 2.0 mol%, relative to the sum of the diphenols used, of trifunctional compounds or higher than the trifunctional ones, for example those having three or more. more than three phenolic groups.

Both homopolycarbonates and copolycarbonates are suitable. The polycarbonates of Component A according to the invention can also be produced using 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 having hydroxy end groups. aryloxy. These are known (reference, for example, US Pat. No. 3 416 634) or can be produced using processes known from the literature. The production of copolycarbonates containing polydiorganosiloxanes is described, for example, in DE-OS 3 334 782.

Preferred polycarbonates, apart from the homopolycarbonates of bisphenol A, are the copolycarbonates of bisphenol A with up to 15 mol%, relative to the sum of moles of the diphenols, of other diphenols mentioned as preferred or particularly preferred, in particular the , 2-bis- (3, 5-dibromo-4-hydroxyphenyl) propane.

The aromatic dicarboxylic acid halides for the production of aromatic polyester carbonates are preferably the diacid dichlorides of isophthalic acid, terephthalic acid, diphenyl ether of 4,4'-dicarboxylic acid and 2,6-naphthalenedicarboxylic acid.

Mixtures of the diacid dichlorides of isophthalic acid and terephthalic acid in a ratio of between 1:20 and 20: 1 are particularly preferred.

A carbonic acid halide, preferably phosgene, is further used as a difunctional acid derivative in the production of polyester carbonates.

The chain terminators which can be considered for the production of aromatic polyester carbonates are, apart from the aforementioned monophenols, also the chlorocarbonic acid esters and the acid chlorides of aromatic monocarboxylic acids, which can optionally be substituted by C alquilo alkyl groups. C22 or by halogen atoms, together with aliphatic C2-C22 monocarboxylic acid chlorides.

The amount of chain terminators is in each case from 0.1 to 10 mol%, in relation, in the case of chain terminators of monocarboxylic acid chloride, to the number of moles of the dicarboxylic acid dichlorides.

The aromatic polyester carbonates may contain incorporated aromatic hydroxycarboxylic acids.

The aromatic polyester carbonates can be both linear and branched in a known manner (reference, in this connection also DE-OS 2 940 024 and DE-OS 3 007 934).

The branching agents which can be used are, for example, tri- or polyfunctional carboxylic acid chlorides, such as trimesic acid trichloride, cyanuric acid trichloride, 3, 3 ', 4,4'-benzophenonecarboxylic acid tetrachloride, tetrachloride. of 1, 5, 8-naphthalenetetracarboxylic acid or pyromellitic acid tetrachloride, in amounts of 0.01 to 1.0% mol (based on the dicarboxylic acid dichlorides used) or tri- or polyfunctional phenols, such as phloroglucinol, 4,6 -dimet il-2,, 6-tri- (4-hydroxy-phenyl) -2-heptene, 4, -dimet-2, 4,6-tri- (4-hydroxyphenyl) heptane, 1, 3, 5- tri- (4-hydroxyphenyl) benzene, 1,1-tri- (4-hydroxyphenyl) ethane, tri- (4-hydroxyphenyl) phenylmethane, 2,2-bis- [4, 4-bis- (4-hydroxyphenyl) ) ciciohexyl] propane, 2,4-bis (4-hydroxyphenylisopropyl) phenol, tetra- (4-hydroxy phenyl) methane, 2,6-bis- (2-hydroxy-5-methylbenzyl) -4-methylphenol, 2- ( 4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane, tetra- (4- [4-hydroxyphenylisopropyl] phenoxy) methane, 1, -bis [4,4'-dihydroxytriphenyl) methyl] benzene, in amounts of 0.01 to 1.0 mol%, based on the diphenols used. The phenolic branching agents can be initially introduced with the diphenols, the acid chloride branching agents can be introduced together with the acid dichlorides.

The portion of the carbonate structural units in aromatic polyester carbonates, thermoplastics may vary. The proportion of the 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 the ester groups and carbonate groups. Both the ester and carbonate fractions of the aromatic polyester carbonates may be in block form or randomly distributed in the polycondensation product.

The viscosity of the relative solution (? Rei) 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 in 100 ml of chloride solution of methylene at 25 ° C).

Aromatic polycarbonates, thermoplastics, and polyester carbonates can be used alone or as any desired mixture with each other.

Component B Component B comprises one or more graft polymers of: B.l of from 5 to 95, preferably from 30 to 80% by weight, of at least one vinyl monomer in B2. from 95 to 5, preferably from 70 to 20% by weight of one or more particular dienes having transition temperatures to the glass of < 10 ° C, preferably from < 0 ° C, particularly preferably from < -20 ° C, which are produced by emulsion polymerization by means of an initiator system comprising organic hydroperoxide and ascorbic acid.

The fundamental grafted B.2 generally has an average particle size (d50 value) of 0.05 to 5 μm, preferably of 0. 10 to 0.6 μm, particularly preferably 0.20 to 0.40 μm.

The monomers B.l are preferably mixtures of: Bll of 50 to 99 parts by weight of vinyl aromatics and / or substituted ring vinyl aromatics (such as, for example, styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) and / or alkyl esters (C? -C8) of methacrylic acid (such as, for example, methyl methacrylate, ethyl methacrylate) and B.1.2 from 1 to 50 parts by weight of vinyl cyanides (unsaturated nitriles such as acrylonitrile and methacrylonitrile) and / or alkyl esters (C? -8) of the acid. { met) acrylic (such as, for example, methyl methacrylate, n-butyl acrylate, t-butyl acrylate) and / or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids (e.g. maleic anhydride and N-phenylmaleimide) ).

The preferred monomers Bll are selected from at least one of the monomers of styrene, α-methylstyrene and methyl methacrylate, the preferred monomers B.1.2 are selected from at least one of the monomers of acrylonitrile, maleic anhydride and methyl methacrylate. .

Particularly preferred monomers are B.l.l. styrene and B.1.2 acrylonitrile.

The preferred basic grafts of B.2 are diene rubbers (for example based on butanediene, isoprene, etc.) or mixtures of diene rubbers or copolymers of diene rubbers or mixtures thereof with additional copolymerizable monomers (for example in accordance with Bll and Bl2), with the proviso that the glass transition temperature of component B.2. be of < 10 ° C, preferably < 0 ° C, particularly preferably from < -10 ° C.

Particularly preferred is the pure polybutadiene rubber.

Particularly preferred graft polymers are those prepared from: a) from 40 to 90% by weight of the particular diene rubber with an average particle diameter of 0.1 to 0.6 μm and b) from 60 to 10% by weight of styrene, acrylonitrile, methyl methacrylate or mixtures thereof by graft emulsion polymerization, which is characterized in that the graft polymerization is carried out using an initiator system comprising an organic hydroperoxide and ascorbic acid to perform a grafted yield of > 60% by weight, preferably > 75% by weight, in particular > 85% by weight (relative to the monomers Bl or b used).

According to a preferred embodiment, the monomers a) are polymerized by grafting in an aqueous emulsion in the presence of an emulsion of the rubber polymer b) at temperatures of 40 to 70 ° C, in particular 50 to 70 ° C, using an initiator system comprising an organic hydroperoxide (I) and ascorbic acid (II), wherein, in general, 0.3 to 1.5 parts by weight of (I) and 0.1 to 1 part by weight of (II) are used. , in each case in relation to 100 parts by weight of a graft monomer and the weight ratio of "(I): (II) is from 0.3 to 15, in particular from 1 to 10, preferably from 3 to 8 (reference DE-A-37 08 913 (= US-A-4,859,744) and EP-A-315 868 (= US-A-, 937, 285)).

The rubbers are generally partially crosslinked and have gel contents of 10 to 90% by weight, in particular 40 to 80% by weight, and are particulate with the average particle sizes (d50 values) of 0.1 to 0.6 μm, in particular from 0.2 to 0.4 μm. Such particulate rubbers are known. These are produced by emulsion polymerization and generally take the form of latices.

The graft polymers are produced in an aqueous emulsion by polymerization of the monomers in a rubber present in the form of an aqueous emulsion. Surface active auxiliaries, emulsifiers or dispersants are conventionally used in this process, optionally together with additives to establish specific pH values and electrolyte contents during graft polymerization. Under certain circumstances, emulsion graft polymerization can also be performed without adding emulsifiers, particularly if the process is run using small amounts of monomers in relation to the amount of rubber, or if the amounts of emulsifier already present in the rubber emulsion (latex) are sufficient in themselves to maintain the graft polymerization of the monomers in the emulsion state with a suitable emulsion stability.

Anionic emulsifiers are particularly suitable, preferably the alkali metal salts of fatty acids, disproportionated resin acids, alkylsulfonic acids, arylsulfonic acids. These are used in amounts of up to 5% by weight, preferably up to 2.5%, relative to the monomers to be polymerized.

Suitable hydroperoxides are, for example, eumenohydroperoxide, tert hydroperoxide. -butyl, hydrogen peroxides, preferably cumene hydroperoxide and tert hydroperoxides. -butyl, that is, hydroperoxides have long half-lives.

An aqueous emulsion of a partially crosslinked diene rubber is batchwise or continuously grafted into an aqueous emulsion; the rubber emulsion is combined with the graft monomers, optionally together with an additional emulsifier, and hydroperoxide together with ascorbic acid solutions at polymerization temperatures of 40 to 70 ° C, in particular 50 to 70 ° C. The number of relationships described above must be maintained during this process. In exceptional cases, small amounts of heavy metal cations, in particular Fe, can be added to the polymerization as an additional component of the initiator system, in particular if it is necessary to use diene rubber emulsions which themselves already contain relatively large amounts. of complex agents. The process runs normally without the addition of iron ions; this method is preferred and advantageously allows the production of graft polymers that virtually do not contain heavy metals or have low heavy metal contents, since such traces of metal are known to have disadvantageous effects on the application properties of plastics. The process is carried out using aqueous solutions of ascorbic acid and aqueous solutions of hydroperoxide; it is advantageous to introduce insufficient water-soluble hydroperoxides, such as cumene hydroperoxide, into the polymerization system in the form of an aqueous emulsion. The emulsifier used in such emulsions is ventingly the same as that used in the graft polymerization.

The hydroperoxide and the ascorbic acid can be partitioned into the graft polymerization in portions or continuously. In a preferred variant, a proportion of the hydroperoxide is initially introduced into the reagents with the rubber to be grafted; the graft monomers together with the remaining ascorbic acid, the hydroperoxide and optionally the emulsifier are introduced separately into the reagent as polymerization processes.

The amounts of hydroperoxide and ascorbic acid are critical. In addition, excessive amounts of hydroperoxide and / or ascorbic acid damage the graft polymerization. Grafting yield drops; the molecular weight of the graft and the reduction of the free resin is reduced; the conversion of the monomer and the stability of the emulsion can also react substantially to the shortages or excesses in the amounts of hydroperoxide or ascorbic acid, making it technically impossible to execute the graft polymerization. It is essential that a temperature of 40 to 70 ° C and the amounts of hydroperoxide / ascorbic acid above are maintained during the graft polymerization in order to optimize the execution of the process, the structure of the grafted polymers and their physical properties. .

When the graft polymerization is continued until monomer conversions of more than 90% by weight, in particular of more than 98% by weight, the storage-stable graft polymer emulsions having polymer contents of 25 to 50% are obtained. in weigh; the graft polymer can be easily isolated from the emulsions by known coagulation processes (for example by means of acids or salts). If it is desired to combine the graft polymers with thermoplastic resins which themselves are in the form of an emulsion, the graft polymer emulsion can be mixed with the resin emulsion and the mixture coagulated.

The gel content of the fundamental graft B.2 is determined in an appropriate solvent (M. Hoffmann, H. Krómer, R. Jun, Polymerana lyt i k I &II, Georg Thieme-Verlag, Stuttgart 1977).

The average particle size d50 is the diameter both above and below which is 50% by weight of the placed particles. This value can be measured by ultracentrifugation (W.

Scholtan, H. Lange, Kol l oi d Z. und Z Polymere, 250 (1972), 782-1796).

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

The appropriate (co) polymers Cl are polymers of at least one monomer from the group of aromatic vinyls, vinyl cyanides (unsaturated nitriles), alkyl (C? -8) esters of (meth) acrylic acid, unsaturated carboxylic acids ( such as anhydrides and imides) of unsaturated carboxylic acids. Particularly suitable (co) polymers are those prepared from: C.1.1 from 50 to 99, preferably from 60 to 80 parts by weight of aromatic vinyls and / or substituted ring aromatic vinyls such as for example styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) and / or alkyl esters (C1-C4) of methacrylic acid such as for example methyl methacrylate, ethyl methacrylate) and C.1.2 from 1 to 50, preferably from 20 to 40 parts by weight of vinyl cyanides (unsaturated nitriles) such as acrylonitrile and (C? -8) alkyl esters of (meth) acrylic acid (such as for example methacrylate of methyl, 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 anhydride and N-phenylmaleimide).

The (co) polymers C.l are resinous thermoplastic and rubber-free The copolymer of styrene C.1.1 and acrylonitrile C.1.2 are particularly preferred.

The (co) polymers C.l are known and can be produced by free radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization. The (co) olimers C.l preferably have molecular weights w (average weight, determined by light scattering or sedimentation) of between 15,000 and 200,000.

The polyalkylene terephthalates of component C.2 are reaction products of aromatic dicarboxylic acids of the reactive derivatives thereof, such as dimethyl esters or anhydrides, and aliphatic, cycloaliphatic or araliphatic diols, together with mixtures of these reaction products.

Preferred polyalkylene terephthalates contain at least 80% by weight, preferably at least 90% by weight, based on the dicarboxylic acid component, terephthalic acid residues and at least 80% by weight, preferably at least 90% by weight, in relation to the diol component, of ethylene glycol and / or residues of 1,4-butanediol.

In addition to the terephthalic acid residues, the preferred polyalkylene terephthalates can contain up to 20 mol%, preferably up to 10 mol%, of residues of other aromatic or cycloaliphatic dicarboxylic acids having from 8 to 14 carbon atoms or aliphatic dicarboxylic acids having from 4 to 12 carbon atoms, such as, for example, residues of phthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid , cyclohexanediacetic acid.

In addition to the residues of ethylene glycol or 1,4-butanediol, the preferred polyalkylene terephthalates can contain up to 20 mol%, preferably up to 10 mol%, of other aliphatic diols having from 3 to 12 carbon atoms or cycloaliphatic diols have from 6 to 21 carbon atoms, for example 1,3-propanediol residues, 2-yl-1,3-propanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol , 3-ethyl -2,4-pentanediol, 2-methyl-2, -pentanediol, 2, 2,4-trimethyl-l, 3-pentanediol, 2-yl-1, 3-hexanediol, 2,2-diethyl -1,3-propanediol, 2,5-hexanediol, 1,4-di- (β-hydroxyethoxy) benzene, 2,2-bis (4-hydroxycyclohexyl) propane, 2,4-dihydroxy- 1, 1, 3, 3-tetramethylcyclobutane, 2,2-bis (4-β-hydroxyethoxyphenyl) propane and 2,2-bis- (4-hydroxypropoxyphenyl) -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 tetrahydric alcohols or tri- or tetrabasic carboxylic acids, for example in accordance with DE-OS 1 900 270 and US-PS 3 692 744. Examples of additional preferred branching agents they are trimesic acid, trimethyl acid, trimethylolethane and trimethylolpropane and pentaerythritol.

Particularly preferred polyalkylene terephthalates are those only produced from terephthalic acid and reactive derivatives thereof (for example dialkyl esters thereof) and ethylene glycol and / or 1,4-butanediol, and mixtures of these polyalkylene terephthalates. .

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

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

Polyalkylene terephthalates can be produced using known methods (reference, for example, Kuns t s t off -Han db u ch, volume VIII, pages 695 and subsequent, Carl Hanser Verlag, Munich 1973).

Component D The phosphazenes of Component D which are used in accordance with the present invention are linear phosphazenes of the formula (la) and cyclic phosphazenes of the formula (Ib) where R and k have the meanings previously established The following may be mentioned by way of example: propoxyphosphazene, phenoxyphosphazene, methylphenoxyphosphazene, methylphenoxyphosphazene, aminophosphazene "and fluoroalkylphosphazene.

Phenoxyphosphazene is preferred.

The phosphazenes can be used alone or as a mixture. The residue R can always be identical or two or more residues in the formula (la) and (Ib) can be different.

Phosphazenes and the production thereof are described, for example, in EP-A 728 811, DE-A 1 961 668 and WO 97/40 092.

Component E The fluorinated polyolefins E are of high molecular weight and have glass transition temperatures above -30 ° C, generally above 100 ° C, fluorine contents preferably from 65 to 76, in particular from 70 to 76% in weight, average particle diameters dso from 0.05 to 1000, preferably from 0.08 to 20 μm. The fluorinated polyolefins E generally have a density of 1.2 to 2.3 g / cm. "The fluorinated polyolefins E are copolymers of polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / hexafluoropropylene and ethylene / tetrafluoroethylene.The fluorinated polyolefins are known (reference, Vi nyl &Related Polymers by Schildknecht, John Wiley &Sons Inc., New York, 1962, pages 484-494; Fl uoropolym ers by Wall, Wiley-Interscience, John Wiley &Sons Inc., New York, volume 13, 1970 , pages 623-654, Modern Pla s ti cs In cycl opedia, 1970-1971, volume 47, No. 10 A, October 1970, McGraw-Hill Inc., New York, pages 134 and 774, Modern Pla s ti cs In Cycl Opedi, 1975-1976, October 1975, Volume 52, No. 10A, McGraw-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 produced using known processes, thus, for example, by polymerizing tetrafluoroethylene in an aqueous medium with a free radical-forming catalyst, for example with sodium, potassium or ammonium peroxydisulfate, at pressures of 7 to 71 kg / cm 2 and a. temperatures from 0 to 200 ° C, preferably at temperatures from 20 to 100 ° C (reference, for example, US Pat. No. 2 393 967 for further details). Depending on the form in which they were used, the density of these materials can be between 1.2 and 2.3 g / cm3, the average particle size between 0.5 and 1000 μm.

Preferred polyolefins E according to the invention are tetrafluoroethylene polymers having average particle diameters of 0.05 to 20 μm, preferably 0.08 to 10 μm, and a density of 1.2 to 1.9 g / cm 3 and are preferably used in the form of a coagulated mixture of emulsions of tetrafluoroethylene polymers E with emulsions of graft polymers B.

Suitable polyolefins E useful in the form of powders are the tetrafluoroethylene polymers having average particle diameters of 100 to 1000 μm and densities of 2.0 g / cm 3 to 2.3 g / cm 3.

A coagulated mixture of B and E is produced first by mixing an aqueous emulsion (latex) of a graft polymer B with a finely divided emulsion of the tetrafluoroethylene polymer E; Conventionally suitable tetrafluoroethylene polymer emulsions have solids contents of from 30 to 70% by weight, in particular from 50 to 60% by weight, preferably from 30 to 35% by weight.

The amount stated in the description of component B may include the proportion of the graft polymer for the coagulated mixture prepared from the graft polymer and the fluorinated polyolefin.

The weight ratio of the graft polymer B to the tetrafluoroethylene polymer E in the emulsion mixture is from 95: 5 to 60:40. The emulsion mixture is then coagulated in a known manner, for example, by spray drying, freeze drying or coagulation by adding inorganic or organic salts, acids, bases or organics, miscible solvents in water, such as alcohols, ketones, preferably at temperatures from 20 to 150 ° C, in particular from 50 to 100 ° C. If necessary, drying can be carried out at 50 to 200 ° C, preferably at 70 to 100 ° C.

Suitable tetrafluoroethylene polymer emulsions are conventional commercial products and are often for sale, for example, by DuPont as Teflon® 30N.

The molding compositions according to the invention may contain at least one of the conventional additives, such as lubricants or mold release agents, nucleating agents, anti-static agents, stabilizers as well as dyes and pigments.

The molding compositions according to the invention can contain up to 35% by weight, relative to the general molding composition, of an optionally additional synergistic flame retardant. Examples of additional flame retardants that may be mentioned are organic halogen compounds, such as decabromobisphenyl ether, tetrabromobisphenol, inorganic halogen compounds such as ammonium bromide, nitrogen compounds, such as melamine, melamine / formaldehyde resins, compounds of inorganic hydroxide, such as Mg, Al hydroxide, inorganic compounds such as antimony oxides, barium metaborate, hydroxoantimonate, zirconium oxide, zirconium hydroxide, molybdenum oxide, ammonium molybdate, zinc borate, ammonium borate, barium metaborate, talc, silicone, silicon dioxide and tin oxide, as well as siloxane compounds.

The molding compositions according to the invention containing component A to E and optionally additional known additives such as stabilizers, dyes, pigments, lubricants and mold release agents, nucleating agents, as well as antistatic agents, are produced by mixing the particular constituents in a known manner and the melt component and the melt-extrudate itself at temperatures from 200 ° C to 300 ° C in conventional units such as mechanical kneaders, extruders and double spin extruders, wherein the E component is preferably used in the form of the aforementioned coagulated mixture.

The individual constituents can be mixed in a known manner both successively and simultaneously and both at about 20 ° C (room temperature) and at a higher temperature.

By virtue of their excellent resistance to flame and very good mechanical properties, the thermoplastic molding compositions according to the invention are suitable for the production of all types of molding, in particular for those requiring high breaking strength.

The molding compositions of the present invention can be used for the production of any type of molding. The mounds can, in particular, be produced by injection molding. Examples of possible misalignments are: frames of all types, for example for domestic applications such as juice extractors, coffee machines, food mixers, for office equipment, such as monitors, printers, copiers or coating sheets for the construction sector and automotive components. These can also be used in electrical engineering applications because of their good electrical properties.

The molding compositions according to the invention can, additionally, for example, be used to produce the following molding or forming articles: Interior seats for rail vehicles (FFCC) 2. Cubes covers 3. Frames for electrical devices that contain small transformers 4. Frames for devices for dissemination and transmission of information 5 Frames and coatings for medical purposes Massage devices and frames for them Toy vehicles for children Elements of wall sheets 9. Frames for security equipment 10. Aerodynamic deflector of the rear composite 11. Thermally insulated transport containers 12. Devices for protecting or caring for small animals 13. Mounts for sanitary and bathing installations 14. Covered grilles for ventilation windows 15 Molds for summer houses and sheds 16 Frames for gardening applications.

Another processing method is the production of slurries by thermally forming the sheets or films produced previously.

The present invention, consequently, also provides for the use of the molding compositions according to the invention for the production of all kinds of molars, preferably those set forth above, and the mounds made from the molding compositions in accordance with the invention. the invention.

Examples Component A Polycarbonate-based linear bisphenol A has a relative solution viscosity of 1252, measured in CH2C12 as a solvent at 25 ° C and a concentration of 0.5 g / 100 ml.

Component B Main Graft B.2 The emulsion of a partially crosslinked coarse particle polybutadiene has an average particle diameter of 0.40 μm (dso value), a gel content of 89% by weight. The emulsion contains 50% by weight of solid polymers Production of graft polymers: Ba) The graft polymer was prepared from 55% by weight of the diene rubber (B.2) and 45% by weight of the SAN copolymer according to DE-A-37 08 913.

A mixture of 200 parts by weight of the latex (B.2) and 149 parts by weight of water are initially introduced into a reactor and heated to 60 to 62 ° C. At this temperature, the following two solutions or emulsions are added to the reactor in the following order: 1. 0.0836 parts by weight of cumene hydroperoxide 6.9600 parts by weight of water 0.0600 parts by weight of Na salt of C14-C16 alkylsulfonic acids 2. 0.0557 parts by weight of ascorbic acid 6.9600 parts by weight of water.

The following was fed and then stirred in the reactor within 4 hours at an internal temperature of 60 to 62 ° C: Zl) 39.05 parts by weight of water 4.00 parts by weight of Na salt of disproportionate acetic acid 3.10 parts by weight of a solution of sodium hydroxide ln 0.62 parts by weight of cumene hydroperoxide Z2) 59 parts by weight of styrene 23 parts by weight of acrylonitrile Z3) 39,800 parts by weight of water 0.105 parts by weight of ascorbic acid The polymerization was then taken to complete at 60 to 62 ° C for a period of 6 hours. The conversion to monomer was greater than 97% by weight.

After stabilization with 1.2 parts by weight of phenolic anti-oxidant per 100 parts by weight of the graft polymer, the graft polymer was isolated by coagulation with a mixture of acetic acid / Mg-sulfate, washed and dried to provide a powder The SAN graft proceeded to a grafting yield of 89% by weight.

The grafting yield was determined by fractional emulsion breaking in an ultracentrifuge using dimethylformamide / methylcyclohexane as the breaking liquids and the amounts of chemical composition of the resulting fractions were determined (reference, Jun, Makrom ol. CEIME 177, 1525 (1976 )).

Bb) Graft polymer prepared from 55% by weight of the diene rubber (B.2) and 4.5% by weight of the SAN copolymer. (Comparative example) The following components were initially introduced into the reactor: 1500 parts by weight of emulsion B.2. and 1030 parts by weight of water. After heating to 65 ° C, an initiator solution comprising 3 parts by weight of potassium peroxodisulfate in 50 parts by weight of water was introduced. The following two solutions were introduced into the reactor at 65 ° C within 6 hours: 1. 442 parts by weight of styrene 172 parts by weight of acrylonitrile 1000 parts by weight of water 13 parts by weight Na salt of disproportionate abietic acid 10 parts by weight of a sodium hydroxide solution In The polymerization was taken to complete within 4 hours with continuous stirring at 65 ° C. The conversion to monomer was greater than 98% by weight. The graft polymer was stabilized and isolated following the procedure for Ba). The SAN graft proceeded to a grafting yield of 55% by weight. The grafting yield was determined in the same way as for Ba).

Component C The styrene / acrylonitrile copolymer has a weight ratio of styrene / acrylonitrile of 72:28 and an intrinsic viscosity of 0.55 dl / g (measured in dimethylformamide at 20 ° C).

Component D The phenoxyphosphazene of the formula Commercial product P-3800 from Nippon Soda Co. Ltd., Japan.

Component E The tetrafluoroethylene polymer as a coagulated mixture prepared from an emulsion of SAN graft polymer corresponding to component B previously established in water and an emulsion of tetrafluoroethylene in water. The weight ratio of the graft polymer B to the tetrafluoroethylene polymer E in the mixture is 90% by weight: 10% by weight. The emulsion of the tetrafluoroethylene polymer has a solids content of 60% by weight, the average particle diameter is between 0.05 and 0.5 μm. The graft polymer emulsion SAN has a solids content of 34% by weight and an average latex particle diameter of d5o = 0.28 μm.

Production of E The emulsion of the tetrafluoroethylene polymer (DuPont 30N Teflon) was mixed with the SAN B graft polymer emulsion and stabilized with 1. 8% by weight, relative to the polymer solids, of phenolic ant i-oxidants. At 85 to 95 ° C, the mixture was coagulated to a pH of 4 to 5 with an aqueous solution of MgSO4 (Epsom salts) and acetic acid, filtered and washed until it was virtually free of electrolytes, then the main amount of Water was removed by centrifugation and the material was then dried at 100 ° C to yield a powder. This powder can be compounded with the other components in the units described.

Production and testing of the mold compositions according to the invention.

The components were mixed in a 3-liter internal mechanical mixer. The moldings were produced at 260 ° C on an Arburg model 270 E injection molding machine.

The Vicat B softness point was determined for DIN 53 460 (ISO 306) in bars of dimensions of 80 x 10 x 4 mm.

The resistance in the welding line was determined by measuring the impact force to DIN 53 453 in the welding line of the test specimens molded by injection on both sides (processing temperature 260 ° C) of dimensions of 170 x 10 x 4 mm.

The behavior of breaking in tension (ESC behavior) was investigated in bars of dimensions of 80 x 10 x 4 mm, processing temperature 260 ° C. The test medium used was a mixture of 60 vol.% Toluene and 40 vol.% Isopropanol. The test pieces were prestressed in a circular arc hearth (initial elongation in percent) and immersed in the test medium at room temperature. The stress breaking behavior was evaluated on the basis of breaking or failure as a function of the initial elongation in the test medium.

The composition and its properties are summarized in Table 1 below.

Table 1: Molding compositions and properties thereof The various improvements in mechanical properties are realized when the special graft polymer produced by means of a reduction oxidation initiator system is used in polycarbonate molding compositions in the presence of phenoxyphosphazene as the flame retardant. High values for the nicked impact force, the strength of the weld line combined with the good resistance to stress cracking are prerequisites for use in thin-walled frame components.

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.

Having described the invention as above, the content of the following is claimed as property.

Claims (18)

Claims

1. Thermoplastic molding compositions, characterized in that they contain: A) from 40 to 99 parts by weight of an aromatic polycarbonate and / or polyester carbonate; B) from 0.5 to 60 parts by weight of graft polymer, characterized in that the graft polymers B comprise: B.l) from 5 to 95% by weight of one or more vinyl monomers and; B.2) from 95 to 5% by weight of one or more particular dienes having a glass transition temperature of < 10 ° C, which are produced by the emulsion polymerization, wherein the graft polymerization is carried out using an initiator system comprising an organic hydroperoxide and ascorbic acid, C) from 0 to 45, parts by weight of at least one thermoplastic polymer selected from the group comprising (co) vinyl polymers and polyalkylene terephthalates, D) from 0.1 to 50 parts by weight of at least one compound selected from the group comprising phosphazenes of the formulas in which R is in each case identical or different and denotes amino, Ci to C8 alkyl, in each case optionally halogenated, or Ci to C8 alkoxy, C5 to C6 cycloalkyl, C to C20 aryl, preferably phenyl or naphthyl, C to C2 aryloxy, preferably C2o; phenoxy, naphthyloxy, or C7 to C2 aralkyl, each optionally substituted by alkyl, and / or halogen, denotes 0 or a number from 1 to 15, E) from 0 to 5, parts by weight of fluorinated polyolefin.

2. The molding compositions according to claim 1, characterized in that they contain 60 to 98.5 parts by weight of A 1 to 40 parts by weight of B 0 to 30 parts by weight of C 2 to 35 parts by weight of D 0.1 to 1 part by weight of E

3. The molding compositions according to claims 1 and 2, characterized in that they contain from 2 to 25 parts by weight of C.

4. The molding compositions according to claims 1 to 3, characterized in that they contain from 5 to 25 parts by weight of D.

5. The molding compositions according to the preceding claims, characterized in that the vinyl monomers B.l are mixtures prepared from B.l.l of 50 to 99 parts by weight of vinyl aromatics and / or substituted ring vinyl aromatics and / or alkyl (C? -8) esters of methacrylic acid and B.1.2 from 1 to 50 parts by weight of vinyl cyanides and / or esters of alkyl (Ci-Cß) of (meth) acrylic acid of unsaturated carboxylic acids.

6. The molding compositions according to the preceding claims, characterized in that the fundamental graft is selected from the diene rubbers or mixtures of diene rubbers or copolymers of diene rubbers or mixtures thereof with additional copolymerizable monomers.

7. The molding compositions according to the preceding claims, characterized in that the fundamental graft is a polybutadiene rubber.

8. The molding compositions according to the preceding claims, characterized in that the yield of the graft in the polymerization is > 60% by weight.

9. The molding compositions according to the preceding claims, characterized in that the graft yield is > 75% in weight.

10. The molding compositions according to the preceding claims, characterized in that the grafting yield is > 85% by weight.

11. The molding compositions according to the preceding claims, characterized in that the cumene hydroperoxide, the tert hydroperoxide. -butyl and / or hydrogen peroxide are used as hydroperoxides.

12. The molding compositions according to the preceding claims, characterized in that the component D is selected from the group consisting of propoxy phosphazene, phenoxyphosphazene, methyl phenoxyphosphazene, aminophosphazene and fluoroalkyl phosphazenes.

13. The molding compositions according to the preceding claims, characterized in that they contain at least one additive selected from the group comprising lubricants and mold releasing agents, nucleating agents, anti-static agents, stabilizers, dyes and pigments.

14. The molding compositions according to the preceding claims, characterized in that they also contain flame retardants that differ from component D.

15. A process for the production of molding compositions according to claim 1, characterized in that components A and E and optionally additional additives are mixed and fused to the compound.

16. The use of the molding compositions according to claim 1, for the production of mounds.

17. The slurries produced from the molding compositions according to claims 1 to 15.

18. The frame parts according to claim 17.