DE4244028A1 - Thermoplastic moulding materials - Google Patents

Abstract

Thermoplastic moulding materials (I) are claimed, based on (A) 10-99 wt.% polyalkylene terephthalate, (B) 5-80 wt.% aromatic polycarbonate, opt. (C) 1-30 wt.% rubber-elastic polymer with Tg below -20 deg. C and/or (D) 0.01-0.5 wt.% phosphite cpd. of formula (II) and/or (E) 0.01-0.5 wt.% phosphorous acid ester of formula (III) and opt. (F) 0.1-1 wt.% nucleating agents, pigments and/or mould release agents. The compsn. contains (G) 8-50 wt.% reprocessed thermoplastic of similar compsn. (A-F). R = 1-18C alkyl, 6-15C aryl, 5-6C cycloalkyl, 7-9C aralkyl or a 1-18C mono-alcohol residue contg. oxetanyl gp(s). (at least one of the R gps. is of this type); Ar = a gp. of formula (IV) (with R1, R2 = H, 1-18C alkyl or mono- or poly-nuclear 6-18C aryl; R3-R6, R3'-R6' = H, 1-18C alk(ox)yl, 3-6C cycloalkyl, mono- or poly-nuclear 6-18C aryl, 1-18C aryloxy or halo); n = 0-10; R7, R8 = 1-9C alkyl, 5-6C cycloalkyl, 7-9C aralkyl or 6-10C aryl; X = -S- or -CH(R9)- (with R9 = 1-6C alkyl or 5-6C cycloalkyl).

Description

The invention relates to thermoplastic molding compositions based on polyalkylene terephthalate, aromatic polycarbonate and optionally rubber-elastic Polymer, the recycled thermoplastic molding compounds accordingly Contain composition, as well as from these thermoplastic molding compositions put molded body.

Mixtures of polyalkylene terephthalate and aromatic polycarbonate or Mi mixtures of polyalkylene terephthalate, aromatic polycarbonate and rubber elastic polymer are known in principle (DE-OS 23 48 377, DE-OS 23 43 609 and EP-A-105 388 and EP-A-373 465).

Thermoplastic mixtures based on polyalkylene are not known terephthalate, aromatic polycarbonate and optionally rubber-elastic Polymer, the reprocessed thermoplastic molding compositions of this together composition included.

As in the literature DIN messages 71.1992, No. 2 - Kunststoffe 80 (1990) 4, Pages 515-517, Plastikververarbeitung 42, 1991, No. 7, Pages 48-52; VDI reports 934, 1991, pages 63-71 - is known to show mixtures of thermoplastics that again contain processed thermoplastic molding compositions of this composition from the original mixture significantly worse level of properties.

The object of the present invention was therefore thermoplastic molding compositions for Ver to provide, which contain refurbished thermoplastic molding compounds and are comparable in their properties to the original mixture.

Surprisingly, it has now been found that thermoplastic mixtures which Reconditioned thermoplastic molding compounds of the appropriate composition contain in their properties correspond to the original mixtures.

The present invention thus relates to thermoplastic molding compositions Base of

• A) 10 to 99, preferably 20 to 80 parts by weight of polyalkylene terephthalate,
• B) 5 to 80, preferably 10 to 60 parts by weight of aromatic polycarbonate,
• C) optionally 1 to 30, preferably 1 to 25 parts by weight of elastomeric polymer having a glass transition temperature (T _g ) of below -20 ° C. and / or
• D) 0.01 to 0.5, preferably 0.05 to 0.4 parts by weight of a phosphite compound of the formula (I) wherein
  RC ₁ -C ₁₈ alkyl, C ₆ -C ₁₅ aryl, C ₅ -C ₆ cycloalkyl, C ₇ -C ₉ aralkyl or for a C ₁ -C ₁₈ monoalko radical containing at least one oxetanyl group, with which Provided that at least one of the radicals R is a C ₁ -C ₁₈ monoalcohol radical containing oxetanyl groups,
  Ar a rest of the formula corresponds to what
  R ¹ and R ^{2 are the} same or different and are hydrogen, C ₁ -C ₁₈ alkyl or mono- or polynuclear C ₆ -C ₁₈ aryl and
  R ³ , R ^{3 '} , R ⁴ , R ^4' , R ⁵ , R ^{5 '} , R ⁶ , R ^{6' are the} same or different and are hydrogen, C ₁ -C ₁₈ alkyl, C ₃ -C ₆ cycloalkyl, are mono- or polynuclear C ₆ -C ₁₈ aryl, C ₁ -C ₁₈ alkoxy, C ₁ -C ₁₈ aryloxy or halogen, and in which
  n is an integer from 0 to 10, and / or
• E) 0.01 to 0.5, preferably 0.05 to 0.4 parts by weight of a phosphoric acid ester of the formula (III) wherein
  R ⁷ and R ^{8 are the} same or different and represent C ₁ -C ₉ alkyl, C ₅ -C ₆ cycloalkyl, C ₇ -C ₉ aralkyl or C ₆ -C ₁₀ aryl and
  X represents -S- or R ⁹ -CH and
  R ^{9 is} hydrogen, C ₁ -C ₆ alkyl or C ₅ -C ₆ cyclohexyl, and
• F) optionally 0.1 to 1 part by weight of nucleating agents, pigments and / or Mold release agents, characterized in that
• G) 8 to 50 parts by weight, preferably 10 to 30 parts by weight, particularly preferably 15 to 25 parts by weight of the molding composition from A) to F) from reprocessed thermoplastic molding compositions, as described under A) to F), where the components A) to G) (A + B + C + D + E + F + G) add up to 100.

Polyalkylene terephthalates A) in the context of the invention are reaction products of aro matic dicarboxylic acids or their reactive derivatives (e.g. dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or araliphatic diols and mixtures of these reaction products.

Preferred polyalkylene terephthalates A) can be obtained from terephthalic acid (or its reactive derivatives) and aliphatic or cycloaliphatic diols with 2 to Produce 10 carbon atoms using known methods (Kunststoff-Handbuch, Vol. VIII, P. 695 ff, Karl-Hanser-Verlag, Munich 1973).

Preferred polyalkylene terephthalates A) contain at least 80, preferably 90 mol%, based on the dicarboxylic acid component, terephthalic acid residues and at least 80, preferably at least 90 mol%, based on the diol composition Nente, ethylene glycol and / or 1,4-butanediol residues.  

The preferred polyalkylene terephthalates A) can in addition to terephthalic acid residues 20 mol% of residues of other aromatic dicarboxylic acids with 8 to 14 carbon atoms or contain aliphatic dicarboxylic acids with 4 to 12 carbon atoms, such as residues of Phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarbon acid, succinic, adipic, sebacic, azelaic, cyclohexanediacetic acid.

In addition to ethylene or butanediol, the preferred polyalkylene terephthalates A) 1,4-glycol residues up to 20 mol% of other aliphatic diols with 3 to 12 carbon atoms or contain cycloaliphatic diols with 6 to 21 carbon atoms, e.g. B. Remains of Pro pandiol-1,3, 2-ethylpropanediol-1,3, neopentylglycol, pentane-diol-1,5, hexanediol-1,6, Cyclohexane-dimethanol-1,4,3-methylpentanediol-2,4,2-methylpentanediol - 2,4,2,2,4- Trimethylpentanediol-1,3 and -1,6,2-ethylhexanediol-1,3,2,2-diethylpropanediol-1,3, Hexanediol-2,5, 1,4-di (β-hydroxyethoxy) benzene, 2,2-bis (4-hydroxycyclohexyl) -pro pan, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis- (3-β-hydroxyethoxyphe nyl) propane and 2,2-bis (4-hydroxypropoxyphenyl) propane (DE-OS 24 07 674, 24 07 776, 27 15 932).

The polyalkylene terephthalates A) can 3- or by incorporating relatively small amounts 4-valent alcohols or 3- or 4-basic carboxylic acid, such as z. B. in DE-OS 19 00 270 and U.S. Patent 3,692,744 are described. Examples preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and propane and pentaerythritol.

It is advisable to use no more than 1 mole% of the branching agent, based on the Acid component to use.

Polyalkylene terephthalates A), which consist solely of terephthalic acid, are particularly preferred and their reactive derivatives (e.g. their dialkyl esters) and ethylene glycol and / or 1,4-butanediol and mixtures of these polyalkylene terephthalate.

Preferred polyalkylene terephthalates A) are also copolyesters which consist of at least two of the above acid components and / or from at least two of the above alcohol components mentioned are produced, particularly preferred copolyesters are poly (ethylene glycol / 1,4-butanediol) terephthalates.  

The polyalkylene terephthalates preferably used as component A) generally an intrinsic viscosity of about 0.4 to 1.5 dl / g, preferably 0.5 to 1.3 dl / g, each measured in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C.

Aromatic polycarbonates B) in the sense of this invention are understood to mean homopoly carbonates, copolycarbonates and mixtures of these polycarbonates, which, for. B. is based on at least one of the following diphenols:
Hydroquinone,
Resorcinol,
Dihydroxydiphenyls,
Bis (hydroxyphenyl) alkanes,
Bis (hydroxyphenyl) cycloalkanes,
Bis (hydroxyphenyl) sulfides,
Bis (hydroxyphenyl) ether,
Bis (hydroxyphenyl) ketones,
Bis (hydroxyphenyl) sulfones,
Bis (hydroxyphenyl) sulfoxides,
α, α′-bis (hydroxyphenyl) diisopropylbenzenes
as well as their nuclear alkylated and nuclear halogenated derivatives.

These and other suitable diphenols are e.g. B. in U.S. Patent 3,028,365, 3,148,172, 2 275 601, 2 991 283, 3 271 367, 3 062 781, 2 970 131 and 2 999 846, in the German Offenlegungsschriften 1 570 703, 2 063 050, 2 063 052, 2 211 956, 2,211,957, French Patent 1,561,518 and in the monograph "H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964 ".

Examples of preferred diphenols are:
2,2-bis (4-hydroxyphenyl) propane,
1,1-bis (4-hydroxyphenyl) cyclohexane,
2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane,
2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane,
2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane,
Bis- (3,5-dimethyl-4-hydroxyphenyl) methane,
Bis (4-hydroxyphenyl) sulfide,
1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.

The diphenols can be used both individually and in a mixture.

Particularly preferred aromatic polycarbonates are polycarbonates based on 2,2-bis (4-hydroxylphenyl) propane or one of the other diphenols mentioned as preferred. Those based on are very particularly preferred
2,2-bis (4-hydroxyphenyl) propane,
2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane or
1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane or mixtures of
2,2-bis (4-hydroxyphenyl) propane and
1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.

The aromatic polycarbonates can be produced by known processes the, e.g. B. by melt transesterification of a corresponding bisphenol with diphenyl carbonate and in solution from bisphenols and phosgene. The solution can be homogeneous be (pyridine process) or heterogeneous (two-phase interface process) (cf. H. Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Vol. IX, Pp. 33 ff, Interscience Publ. 1964).

The aromatic polycarbonates generally have average molecular weights _w of approximately 10,000 to 200,000, preferably 20,000 to 80,000 (determined by gel chromatography after prior calibration).

Copolycarbonates in the sense of the invention are in particular polydiorganosiloxane-polycarbonate block copolymers with an average molecular weight _w of approximately 10,000 to 200,000, preferably 20,000 to 80,000 (determined by gel chromatography after prior calibration) and with a content of aromatic carbonate structural units of approximately 75 to 97.5% by weight, preferably 85 to 97% by weight and a content of polydiorganosiloxane structural units of approximately 25 to 2.5% by weight, preferably 15 to 3% by weight, the block copolymers starting from α, Polydiorganosiloxanes containing ω-bishydroxyaryloxy end groups, with a degree of polymerization P _n of 5 to 100, preferably 20 to 80, can be produced.

The polydiorganosiloxane-polycarbonate block copolymers can also have a Mi polydiorganosiloxane-polycarbonate block copolymers with common polysi be loxane-free, thermoplastic polycarbonates, the total content of poly diorganosiloxane structural units in this mixture is approximately 2.5 to 25% by weight.

Such polydiorganosiloxane-polycarbonate block copolymers are known records that they have aromatic carbonate structural units in the polymer chain (1) and on the other hand contain aryloxy end group-containing polydiorganosiloxanes (2),

wherein
Ar are identical or different aryl residues from diphenols and
R ¹⁰ and R ^{11 are the} same or different and are linear alkyl, branched alkyl, alkenyl, halogenated linear alkyl, halogenated branched alkyl, aryl or halogenated aryl, preferably methyl, and
The number of diorganosiloxy units is m + a + b + c = 5 to 100, preferably 20 to 80.

Alkyl in the above formula (1) is, for example, C ₁ -C ₂₀ -alkyl, alkenyl in the above formula (1) is, for example, C ₂ -C ₆ -alkenyl; Aryl in the above formula (1) is C ₆ -C ₁₄ aryl. Halogenated in the above formula means partially or completely chlorinated, brominated or fluorinated. Examples of alkyls, alkenyl, aryls, halogenated alkyls and halogenated aryls are methyl, ethyl, propyl, n-butyl, tert-butyl, vinyl, phenyl, naphthyl, chloromethyl, perfluorobutyl, perfluorooctyl and chlorophenyl.

Such polydiorganosiloxane-polycarbonate block copolymers are e.g. B. from US-PS 3,189,662, U.S. Patent 3,821,325 and U.S. Patent 3,832,419.

Preferred polydiorganosiloxane-polycarbonate block copolymers are produced by combining α, ω-bishydroxyaryloxy end group-containing polydiorganosiloxanes men with other diphenols, possibly with the use of chain breakers chern in the usual amounts and, if necessary, with the use of Branch in the usual amounts, e.g. B. after the two-phase limit surface method (see H. Schnell, Chemistry and Physics of Polycarbonates Poly mer Rev. Vol. 15, page 27 ff, Interscience Publishers New York 1964), where the ratio of the bifunctional phenolic reactants chosen in each case that the aromatic carbonate structure content according to the invention units and diorganosiloxy units results.

Such α, ω-bishydroxyaryloxy end group-containing polydiorganosiloxanes are z. B. known from US-PS 34 19 634.

The rubber-elastic polymers C) comprise copolymers - in particular Graft copolymers - with rubber-elastic properties that are essentially are available from at least 2 of the following monomers:

Chloroprene, isoprene, isobutene, styrene, acrylonitrile, ethylene, propylene, vinyl acetate and (meth) acrylic acid esters with 1 to 18 carbon atoms in the alcohol component; so Polymers such as z. B. in "Methods of Organic Chemistry" (Houben-Weyl), Vol. 14/1, Georg-Thieme-Verlag, Stuttgart 1961, pp. 393 to 406 and in C.B. Bucknall, "Thoughened Plastics," Appl. Science Publishers, London 1977, be are written. The polymers C) have a gel content of more than 20, preferably wise over 40% by weight. The glass transition temperature (Tg) is below -20 ° C.  

Preferred polymers C) are selectively hydrogenated block copolymers of a vinyl aromatic monomers (X) and a conjugated diene (Y) of the X-Y type. This Block copolymers can be prepared by known processes.

In general, suitable for the preparation of suitable X-Y block copolymers Styrene, α-methylstyrene, vinyltoluene etc. and from conjugated dienes such as butadiene, Isoprene, etc., used for the production of styrene-diene block polymers Technology used in "Encyclopedia of Polymer Science and Technology ", vol. 15, Interscience, N.Y. (1971) on pages 508 ff. The selective hydrogenation can be carried out in ways known per se and means that the ethylenic double bonds are essentially completely hydrogenated are, the aromatic double bonds essentially unaffected stay.

Such selectively hydrogenated block copolymers are, for. B. in DE-OS 30 00 282.

Preferred polymers C) are, for. B. with styrene and / or acrylonitrile and / or (Meth) acrylic acid alkyl esters grafted polybutadienes, butadiene / styrene copolymers sate and poly (meth) acrylic acid esters, e.g. B. copolymers of styrene or alkyl styrene and conjugated dienes (impact resistant polystyrene), d. H. Copolymers of the OS 16 94 173 (= US-PS 35 64 077) described type, with acrylic or Methacrylic acid esters, vinyl acetate, acrylonitrile, styrene and / or alkylstyrenes grafted polybutadienes, butadiene / styrene or butadiene / acrylonitrile copolymers, Polyisobutane or polyisoprene, such as z. B. in DE-OS 23 48 377 (= US-PS 3 919 353) or in DE-A-31 05 264 and DE-A-30 19 233.

Particularly preferred polymers C) are, for. B. ABS polymers (both mixed as well as graft types), such as. B. in DE-OS 20 35 390 (= US-PS 36 44 574) or in DE-OS 22 48 242 (= GB-PS 1 409 275) are described.

In addition, particularly preferred polymers C) are graft polymers which by grafting reaction of

• I. 10 to 40, preferably 20 to 35% by weight, based on the graft product, of at least one (meth) acrylic acid ester and / or a mixture of
  10 to 40, preferably 20 to 35 wt .-% based on the mixture, acrylonitrile and
  60 to 90, preferably 65 to 80% by weight, based on the mixture, of styrene
• II. 60 to 90, preferably 65 to 90% by weight, based on the graft product, of one Butadiene polymer with at least 70 wt .-% based on II, butadiene residues are available as a graft base,

preferably the gel fraction of the graft base II 70% (measured in toluene), the degree of graft G 0.15 to 0.55 and the average particle diameter d _{50 of} the graft polymer C) 0.2 to 0.6, preferably 0.3 to 0 . 5 µm (see, for example, EP-01 31 202).

(Meth) acrylic acid esters I are esters of acrylic acid or methacrylic acid and one tiger alcohols with 1 to 8 carbon atoms.

In addition to butadiene residues, the graft base II can contain up to 30% by weight, based on II, Residues of other ethylenically unsaturated monomers such as. B. styrene, acrylonitrile, ester of acrylic or methacrylic acid with 1 to 4 carbon atoms in the alcohol component (as Methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate). The be preferred graft base II consists of pure polybutadiene.

As is known, in the graft reaction, the graft monomers I do not completely react to the Grafting on graft base II are, according to the invention, under graft polymers also understood those products that, in addition to the actual graft polymers also contain homopolymers and copolymers of the graft monomers I used.

The degree of grafting G denotes the weight ratio of grafted grafted mono mer to the graft base and is dimensionless.

The average particle size d ₅₀ is the diameter above and below which 50% by weight of the particles lie. It can be determined by means of ultracentrifuge measurements (W. Scholtan, H. Lange, Kolloid Z. and Z. Polymer 250 (1972), 782-796) or by means of electron microscopy and subsequent particle counting (C. Kämpf, H. Schuster, Angew Macromolecular Chemistry 14, (1970), 111-129) or by means of light scatter measurements).

Particularly preferred polymers C) are, for. B. also from graft polymers

• a) 25 to 98 wt .-% based on C), acrylate rubber with a glass transition temperature below -20 ° C as graft base and
• b) 2 to 75% by weight, based on C), of at least one polymerizable, ethyl nisch unsaturated monomers, whose or in the absence of (a) ent existing homopolymers or copolymers have a glass transition temperature of 25 ° C, as graft monomers.

The acrylate rubbers (a) of the polymers C) are preferably polymers of alkyl acrylates, optionally with up to 40% by weight of other polymerizable, ethylenically unsaturated monomers. If the acrylate rubbers used as the graft base (a) are graft products with a diene rubber core, as described below, the diene rubber core is not included in the calculation of this percentage. The preferred polymerizable acrylic acid esters include C ₁ -C ₈ alkyl esters, for example methyl, ethyl, butyl, octyl and 2-ethylhexyl esters; Halogen alkyl esters, preferably halogen C ₁ -C ₈ alkyl esters such as chloroethyl acrylate and aromatic esters such as benzyl acrylate and phenethyl acrylate. They can be used individually or in a mixture.

The acrylate rubbers (a) can be uncrosslinked or crosslinked, preferably partially to be connected.

Monomers with more than one polymerizable double can be used for crosslinking bond are copolymerized. Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids with 3 to 8 carbon atoms and more saturated monohydric alcohols with 3 to 12 carbon atoms or saturated polyols with 2 to 4 OH Groups and 2 to 20 carbon atoms, such as. B. ethylene glycol dimethacrylate, allyl meth acrylate, polyunsaturated heterocyclic compounds, such as. B. trivinyl and  Triallyl cyanurate and isocyanurate, trisacryloyl-s-triazine, especially triallyl cyanurate; polyfunctional compounds such as di- and trivinylbenzenes; but also Triallyl phosphate and diallyl phthalate Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimeth acrylate, diallyl phthalate and heterocyclic compounds containing at least 3 ethy have lenically unsaturated groups.

The cyclic monomers triallyl are particularly preferred crosslinking monomers cyanurate, triallyl isocyanurate, trivinyl cyanurate, triacryloylhexahydro-s-triazine, tri allylbenzenes.

The amount of the crosslinking monomers is preferably 0.02 to 5, in particular especially 0.05 to 2% by weight based on the graft base (a).

For cyclic crosslinking monomers with at least 3 ethylenically unsaturated It is advantageous for groups to increase the amount to <1% by weight of the graft base (a) restrict.

Preferred "other" polymerizable, ethylenically unsaturated monomers which, in addition to the acrylic acid esters, can optionally be used to prepare the graft base (a) are, for. B. acrylonitrile, styrene, α-methylstyrene, acrylamides, vinyl C ₁ -C ₆ alkyl ether. Preferred acrylic rubbers as the graft base (a) are emulsion polymers which have a gel content of 60% by weight.

The gel content of the graft base (a) is determined at 25 ° C. in dimethylformamide (M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik I and II, Georg Thieme Verlag, Stuttgart 1977).

Acrylic rubbers as a graft base (a) can also be products that ver wetted diene rubber from one or more conjugated dienes, such as poly butadiene, or a copolymer of a conjugated diene with an ethylenically un saturated monomer, such as styrene and / or acrylonitrile, as the core.  

The proportion of the polydiene core in the graft base (a) can be 0.1 to 80, preferably 10 to 50 wt .-% based on (a). Shell and core can be independent not cross-linked, partially cross-linked or highly cross-linked.

The aforementioned graft polymers made of poly are very particularly preferred butadiene as a graft base and (meth) acrylic acid ester and acrylonitrile as a graft edition, wherein the graft base from 65 to 90 wt .-% parts of crosslinked poly butadiene with a gel content of over 70% (in toluene) and the graft base a 5: 1 to 201 mixture of methyl methacrylate and n-butyl acrylate (e.g. DE-31 05 364, DE-30 19 233).

Phosphite compounds (component D)) in the context of the invention are compounds of formula (I)

wherein
RC ₁ -C ₁₈ alkyl, C ₆ -C ₁₅ aryl, C ₅ -C ₆ cycloalkyl, C ₇ -C ₉ aralkyl or for a C ₁ -C ₁₈ monoalko radical containing at least one oxetanyl group, with which Provided that at least one of the radicals R is a C ₁ -C ₁₈ monoalcohol radical containing oxetanyl groups,
Ar a rest of the formula

corresponds to what
R ¹ and R ^{2 are the} same or different and are hydrogen, C ₁ -C ₁₈ alkyl or mono- or polynuclear C ₆ -C ₁₈ aryl and
R ³ , R ^{3 '} , R ⁴ , R ^4' , R ⁵ , R ^{5 '} , R ⁶ , R ^{6' are the} same or different and are hydrogen, C ₁ -C ₁₈ alkyl, C ₃ -C ₆ cycloalkyl, are mono- or more nuclear C ₆ -C ₁₈ aryl, C ₁ -C ₁₈ alkoxy, C ₁ -C ₁₈ aryloxy or halogen,
and in what
n is an integer from 0 to 10, preferably from 0 to 2.

Phosphoric acid esters (component E)) in the context of the invention are compounds of Formula (III)

wherein
R ⁷ and R ^{8 are the} same or different and are C ₁ -C ₉ alkyl, C ₅ -C ₆ cycloalkyl, C ₇ -C ₉ aralkyl or C ₆ -C ₁₀ aryl and
X represents -S- or R ⁹ -CH and
R ^{9 is} hydrogen, C ₁ -C ₆ alkyl or C ₅ -C ₆ cyclohexyl.

Examples of alkyl radicals of the formulas (I), (II) and (III) are: methyl, ethyl, propyl, isononyl;
as aralkyl residues:

as cycloalkyl radicals: cyclopentyl, cyclohexyl;
as aryl radicals: phenyl, naphthyl;
as alkoxy radicals: methoxy, ethoxy, propoxy, butoxy;
as aryloxy radicals: phenoxy, naphthoxy;
and as halogens: fluorine, chlorine, bromine, preferably fluorine and chlorine.

Phosphite compounds (D) of the formula (I) in which
n = 0 means
Ar for

stands.

Phosphorous acid- (1-methylethylene) -di-4, 1-phenylene is very particularly preferred tetrakis-3-ethyl- (3-oxethanyl) methyl) ester.

As component E), preference is given to using phosphorous acid esters of the formula (III) in which R ⁷ and R ^{8 are} benzyl, α, α-dimethylbenzyl, methyl, ethyl, isopropyl, tert-butyl, tert. -Amyl, isononyl, cyclopentyl or cyclohexyl radical and X is

stands.

The phosphorous acid ester of the formula (III) is particularly preferred, where X is methylene, R ^{7 is} cyclohexyl and R ^{8 is} methyl [4,8-dicyclohexyl-6-hydroxy-2,10-dimethyl-12H-dibenzo (d, g ) (1,3,2) -dioxaphosphocin].

The phosphite compounds of the formula (I) can be prepared in a known manner Transesterification of corresponding phosphites with diphenols (which differ from formula (II) derive) are produced (see. DE-OS 25 10 463).

The phosphorous acid esters of the formula (III) can be prepared in a known manner by reacting triphenyl phosphite with the corresponding dihydroxyverbin dungen in the presence of water (see, for example, DE-OS 29 29 229).

The molding materials can nucleating agents such as finely divided carbon black and microtalk contain. In addition, the molding compositions can contain conventional additives such as slip and defor contain fillers and reinforcing materials as well as dyes and pigments.

The nucleating agents and additives can be used in amounts of approximately 0.1 to 1.0% by weight. Parts of the molding compositions according to the invention are added.

Reconditioned thermoplastic molding compounds of the appropriate composition tion in the sense of the invention are thermoplastic molding compositions which are composed of the compo nents are composed as described on pages 2-16, and before their Ver application have been exempted from a coating adhering to the original state. This coating can e.g. B. a plastic layer, a color layer, a metal layer but also be a layer of paint, such as z. B. on bumpers in the automotive sector  is found and / or a combination of these layers. The elimination of the Coating can be done using various methods. So it is possible Remove coatings both chemically and mechanically. In the mechanical Various methods are suitable for removal, e.g. B. grinding, brushing or Radiate.

The process of chemical removal is particularly characterized by that the polycondensate waste by means of a shredder or a mill, as in the Literature is described (see for example "Ullmanns Encyklopadie der technical chemistry, 4th edition (1972), volume 2, process engineering I (reason operations), SS 2 to 34 ′ ′), crushed with acid to reflux under Stirring be heated, neutral with water in such a way with gentle stirring be washed that the separated from the polycondensate, but not yet dissolved paint components are rinsed out of the polycondensate, the polycondensate after the filtering of the water in the usual drying apparatus, as they for example in "Ullmann's Encyclopedia of Industrial Chemistry, 4th edition (1972), Volume 2, Process Engineering I (basic operations), SS 699 to 721 "are described, dried and, if necessary, subsequently by air sifting with apparatus, such as she, for example, in "Ullmanns Encyklopadie der Technische Chemie, 4th edition (1972), Volume 2, Process Engineering 1 (basic operations), SS 57 to 69 are, possibly from the remaining paint residues or dye residues be separated (see, for example, EP-A 476 475). In all the cases where the Polycondensate waste does not naturally contain metals, these are separated, added, for example, as a powder before the acid, if appropriate also in the form of Metal salts.

It is in particular a process for cleaning waste from thermoplastic, aromatic polycarbonates and / or thermoplastic, aromatic polyester carbonates, the metals - optionally in the form of metal salts -, lacquers and optionally contain dyes, which is characterized in that the Waste into fragments with an average diameter of 0.1 cm to 5.0 cm, preferably from 0.5 cm to 1.5 cm, crushed, then these fragments with acid on Reflux heated with stirring, then washed neutral with water with stirring and finally rinse with water until all those separated from the polycondensate  Parts of the paint are rinsed out, the fragments are filtered off, dried and, if necessary by air sighting the paint and / or still adhering to the fragments Separates dye residues.

By treating the polycondensate waste with acid after dissolving the Most of the paints are also separated from the polycarbonates and metals even partially dissolved.

This effect occurs without the presence of a metal such as aluminum not one, because without aluminum reactive species like nascent hydrogen and Aluminum (III) salts cannot be formed "in situ".

In addition to aluminum, metals suitable for the cleaning process are iron and zinc and tin. However, iron, zinc and tin act in a weakened form in comparison to aluminum.

Paints that detach from the polymer and partially dissolve after the process are, for example, those based on polyacrylonitrile, polyacrylate, polymethacrylate, Polyvinyl chloride, polysiloxane or melamine resin based.

Dyes suitable for the cleaning process are, for example, those based on of naphthaquinones, benzoquinones, anthraquinones and azo compounds, and organic pigments and inorganic pigments such as iron oxides, chromium oxides and Titanium dioxide.

Polyalkylene terephthalates, such as. B. Polybutylene terephthalate is mechanically raised works because they tend to decompose in chemical reprocessing methods.

In particular, there is a process for cleaning waste thermoplastic, aromatic polycarbonates and / or thermoplastic, aromatic polyester carbonates, the metals - optionally in the form of metal contain salts, lacquers and optionally dyes as surface coating, which is characterized in that the waste is added if necessary Fragments of an average diameter of 0.1 to 5.0 cm, preferably from 0.4 to 1.5 cm crushed, then these fragments in an irradiation chamber  is directed or if necessary subjected to all-round particle radiation, which removes the adhering surface coatings.

Both sand and metal grains with very small particles come as blasting particles Dimensions in question.

That formed from the blasting particles and the particles of the surface coating Mixture is then separated and discharged in such a way that none Residues the quality of the pure thermoplastic, aromatic obtained Polycarbonate and / or thermoplastic, aromatic polyester carbonate in the Disrupt further processing.

The methods are state of the art (DE-OS 15 77 537, US-P 33 92 491 and DE-OS 23 38 994 A1).

The recycled components of the thermoplastic molding compositions correspond The composition according to the invention can in the original state, ie. H. before reprocessing as molded articles in various applications have been used. So you can z. B. in the automotive sector as a bumper or Outside mirrors, or used in the electronics sector as compact discs his.

The remanufactured thermoplastic molding compounds corresponding together Settlement in the sense of the invention can in the original state, d. H. before again preparation have been used as moldings in various applications. So you can z. B. in the automotive sector as an outside mirror, door sills, bumper, Windshield wipers and many other applications. Next They can also be used in the automotive sector in the household and electrical / electronic Area.

The molding compositions according to the invention can also contain conventional additives such as Lubricants and mold release agents, stabilizers, fillers and reinforcing materials as well Dyes are added.  

The additives can in amounts of about 0.1 to 5.0 parts by weight according to the Invention moderate molding compositions are added.

The molding compositions according to the invention can be prepared in the customary mixture aggregates such as rollers, kneaders, single or multi-shaft extruders by mixing of the individual components can be obtained.

Examples Components used

• A) Polybutylene terephthalate (PBT)
  Intrinsic viscosity IV = 1.19 ± 0.03
• B) Linear polycarbonate (PC) based on bisphenol A with a relative solution viscosity η _rel of 1.29 ± 0.015
• C) Graft polymer
  Graft copolymer, an emulsion polymer made from 80 parts by weight of crosslinked polybutadiene (gel content over 70%, measured in toluene) and 20 parts by weight of graft made from 18 parts by weight of methyl methacrylate and 2 parts by weight of n-butyl acrylate, the middle Particle diameter of the graft base present in latex form is between 0.3 and 0.5 μm (see information in DE-OS 31 05 364 and DE-OS 30 19 233).
  • I: composition:
    58% by weight PBT,
    21% by weight PC,
    21% by weight of graft polymer.
  • II: Refurbished material of composition I; processed after mechanical particle radiation.
  • III: Refurbished material of composition I, lacquered, ground.

In the following, Examples 1 and 3 are comparative examples. Example 2 is inventive according to.  

table

Claims (3)

1. Thermoplastic molding compositions based on

• A) 10 to 99 parts by weight of polyalkylene terephthalate,
• B) 5 to 80 parts by weight of aromatic polycarbonate,
• C) optionally 1 to 30 parts by weight of rubber-elastic polymer with a glass transition temperature (T _g ) of below -20 ° C and / or
• D) 0.01 to 0.5 part by weight of a phosphite compound of the formula (I) wherein
  RC ₁ -C ₁₈ alkyl, C ₆ -C ₁₅ aryl, C ₅ -C ₆ cycloalkyl, C ₇ -C ₉ aralkyl or represents a C ₁ -C ₁₈ monoalcohol radical containing at least one oxetanyl group, with the proviso that at least one of the radicals R represents a C ₁ -C ₁₈ monoalcohol radical containing oxetanyl groups,
  Ar a rest of the formula corresponds to what
  R ¹ and R ^{2 are the} same or different and are hydrogen, C ₁ -C ₁₈ alkyl or mono- or polynuclear C ₆ -C ₁₈ aryl and
  R ³ , R ^{3 '} , R ⁴ , R ^4' , R ⁵ , R ^{5 '} , R ⁶ , R ^{6' are the} same or different and are hydrogen, C ₁ -C ₁₈ alkyl, C ₃ -C ₆ cycloalkyl, are mono- or polynuclear C ₆ -C ₁₈ aryl, C ₁ -C ₁₈ alkoxy, C ₁ -C ₁₈ aryloxy or halogen,
  and in what
  n is an integer from 0 to 10, and / or
• E) 0.01 to 0.5 part by weight of a phosphorous acid ester of the formula (III) wherein
  R ⁷ and R ^{8 are the} same or different and represent C ₁ -C ₉ alkyl, C ₅ -C ₆ cycloalkyl, C ₇ -C ₉ aralkyl or C ₆ -C ₁₀ aryl and
  X represents -S- or R ⁹ -CH and
  R ^{9 is} hydrogen, C ₁ -C ₆ alkyl or C ₅ -C ₆ cyclohexyl, and
• F) optionally 0.1 to 1 part by weight of nucleating agents, pigments and / or mold release agents, characterized in that
• G) 8 to 50 parts by weight of the molding composition from A) to F) consist of recycled thermoplastic molding compositions, as described under A) to F), the components A) to G) (A + B + C + Add D + E + F + G) to 100.

2. Thermoplastic molding compositions according to claim 1, which 20 to 80 parts by weight A), 10 to 60 parts by weight of B), optionally 1 to 25 parts by weight of C), 0.05 to 0.4 parts by weight D) and 0.05 to 0.4 parts by weight E) included. 3. Use of remanufactured thermoplastic molding compositions, as under 2A) to F) according to claim 1, for the production of thermoplastic molding compounds from components A) to F), that 8 to 50 parts by weight of recycled molding compound is incorporated.