DE4244027A1 - Thermoplastic moulding materials with reprocessed polymer components - Google Patents

Abstract

Thermoplastic moulding materials (I) are claimed, based on (A) 1-99 wt.% polyalkylene terephthalate, (B) 0-80 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) 5-80 wt.% reprocessed thermoplastic of type (A), (B) and/or (C), which is not mixed with other thermoplastics. In formulae, 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 (I) (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 6-19C aryl; X = -S- or -CH(R9)- (with R9 = H, 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 reprocessed thermoplastic Molding compositions contain this composition, as well as this thermoplastic molding compound body.

Mixtures of polyalkylene terephthalate and aromatic Polycarbonate or mixtures of polyalkylene terephthalate lat, aromatic polycarbonate and rubber elastic Basically, polymers are known (DE 23 48 377, DE 23 43 609 and EP-A 105 388 and EP-A 373 465).

Thermoplastic mixtures based are not known of polyalkylene terephthalate, aromatic polycarbonate and optionally rubber-elastic polymer, the Reconditioned thermoplastic molding compounds Composition included.  

As in the literature DIN message 71.1992, No. 2 - Kunststoffe 80 (1990) 4 (page 515-517), Plastikver worker 42 1991 No. 7 page 48-52; VDI reports 934 1991 page 63-71 - is known, show mixtures of Thermoplastics the reconditioned thermoplastic Molding compositions containing this composition, one of the Original mixture significantly worse property level.

The object of the present invention was therefore to maintain to provide parts of the molding compositions which remanufactured thermoplastic components Contain molding compound of appropriate composition and in their properties with the original blend are comparably good.

It has been found that thermoplastic mixtures that one or more remanufactured components (pure polycarbonate or pure polybuty terephthalate lat) corresponding to the thermoplastic molding composition Composition, contained in their properties Original mixtures correspond. With these mixtures may be part of the original thermoplastic molding compound in whole or in part by one again reconditioned part of the thermoplastic form mass have been replaced.

The present invention thus relates to thermo plastic molding compounds based on

• A) 1 to 99, preferably 20 to 80 parts by weight of poly alkylene terephthalate,
• B) 0 to 80, preferably 10 to 60 parts by weight aromatic polycarbonate,
• C) optionally 1 to 30, preferably 1 to 25 Parts by weight of rubber-elastic polymer a glass transition temperature (Tg) 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 wherein
  RC ₁ -C ₁₈ alkyl, C ₆ -C ₁₅ aryl, C ₅ -C ₆ cycloalkyl, C ₇ -C ₉ aralkyl, or a C ₁ -C ₁₈ monoalko radical containing at least one oxetanyl group, with with the proviso 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, and / or
• E) 0.01 to 0.5, preferably 0.05 to 0.4 parts by weight of a phosphorous acid ester of the formula 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 ₁₉ aryl
  and
  X represents -S- or R ⁹ -CH, wherein R ^{9 represents} hydrogen, C ₁ -C ₆ alkyl or C ₅ -C ₆ cyclohexyl, and
• F) optionally 0.1 to 1 part by weight of nucleation agents, pigments and / or mold release agents,

characterized in that

• G) 5 to 80 parts by weight, preferably 5 to 50, ins special 5 to 25 parts by weight of a reprocessed did not ride mixed with other thermoplastics th thermoplastic component according to A), B) and / or C) in the molding composition from A) to F) are set, the components A) to G) Add (A + B + C + D + E + F + G) to 100.

Polyalkylene terephthalates A are in the sense of the invention Reaction products from aromatic dicarboxylic acids or their reactive derivatives (e.g. dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or araliphatic diols and mixtures of this reac tion products.  

Preferred polyalkylene terephthalates A can be selected from Terephthalic acid (or its reactive derivatives) and aliphatic or cycloaliphatic diols with 2 produce up to 10 carbon atoms by known methods (Kunststoff-Handbuch, Vol. VIII, p. 695 ff, Karl-Hanser- Verlag, Munich 1973).

Preferred polyalkylene terephthalates A contain min at least 80, preferably 90 mol% based on the Dicarboxylic acid component, terephthalic acid residues and min at least 80, preferably at least 90 mol%, based on the diol component, ethylene glycol and / or butane diol 1,4 residues.

The preferred polyalkylene terephthalates A can besides Terephthalic acid residues up to 20 mol% residues of others aromatic dicarboxylic acids with 8 to 14 carbon atoms or aliphatic dicarboxylic acids with 4 to 12 carbon atoms hold, like residues of phthalic acid, isophthalic acid, Naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarbon acid, succinic, adipic, sebacic, azelaic, Cyclohexanediacetic acid.

The preferred polyalkylene terephthalates A can besides Ethylene or 1,4-butanediol glycol residues up to 20 mol% other aliphatic diols with 3 to 12 carbon atoms or Contain cycloaliphatic diols with 6 to 21 carbon atoms ten, e.g. B. Residues of propanediol-1,3,2-ethylpropanediol- 1,3, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 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) propane, 2,4-dihydroxy 1,1,3,3-tetramethyl-cyclobutane, 2,2-bis (3-β-hydroxy ethoxyphenyi) propane and 2,2-bis (4-hydroxypropoxy phenyl) propane (DE-OS 24 07 674, 24 07 776, 27 15 932).

The polyalkylene terephthalates A can by rela tiv small amounts of 3- or 4-valent alcohols or 3- or 4-basic carboxylic acid as z. B. in DE-OS 19 00 270 and U.S. Patent 3,692,744, be branched. Examples of preferred branching middle are trimesic acid, trimellitic acid, trimethylol ethane and propane and pentaerythritol.

It is advisable to use no more than 1 mole% of the branch means to use, based on the acid component.

Particularly preferred are polyalkylene terephthalates A which solely from terephthalic acid and its reactive Derivatives (e.g. their dialkyl esters) and ethylene glycol and / or 1,4-butanediol have been prepared, and Mixtures of these polyalkylene terephthalates.

Preferred polyalkylene terephthalates A are also copoly esters consisting of at least two of the abovementioned acid Components and / or from at least two of the above named alcohol components are made, especially preferred copolyesters are poly (ethylene glycol / butane) diol-1,4) terephthalates.  

The poly preferably used as component A. Alkylene terephthalates generally have one Intrinsic viscosity of approximately 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 homopolycarbonates, 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. Tie U.S. Patent 3,028,365, 2,999,835, 3,148,172, 2,275,601, 2 991 283, 3 271 367, 3 062 781, 2 970 131 and 2,999,846, in German Offenlegungsschriften 15 70 703, 20 63 050, 20 63 052, 22 11 956, 22 11 957  French Patent 1,561,518 and in Monograph "H. Schnell, Chemistry and Physics of Poly carbonates, Interscience Publishers, New York 1964 ", be wrote.

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 individually or in a mixture be used.

Aromatic polycarbonates are particularly preferred Polycarbonates based on 2,2-bis (4-hydroxy phenyl) propane or one of the others as preferred called diphenols. Are very particularly preferred those based on 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane or 1,1- Bis- (4-hydroxyphenyl) -3,3,5-trimethylcycloxane or Mixtures of 2,2-bis (4-hydroxyphenyl) propane and 1,1- Bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.

The aromatic polycarbonates can according to known Processes are made, e.g. B. by Schmelzum  esterification of a corresponding bisphenol with diphenyl carbonate and in solution from bisphenols and phosgene. The Solution can be homogeneous (pyridine process) or heterogeneous (two-phase interface method) (cf. M. Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Vol. IX, pp. 33 ff, Interscience Publ. 1964).

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

Copolycarbonates for the purposes of the invention are in particular polydiorganosiloxane-polycarbonate block copolymers with an average molecular weight M _w of approximately 10,000 to 200,000, preferably 20,000 to 80,000 (determined by gel chromatography after prior calibration) and with an aromatic carbonate structural unit content 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, ω-bishydroxy aryloxy end groups -containing polydiorganosiloxanes with a degree of polymerization P _n of 5 to 100, preferably 20 to 80, can be produced.

The polydiorganosiloxane-polycarbonate block polymers can also be a mixture of polydiorganosiloxane poly carbonate block copolymers with conventional polysiloxane free, thermoplastic polycarbonates, the  Total content of polydiorganosiloxane structural units in this mixture is approximately 2.5 to 25% by weight.

Such polydiorganosiloxane-polycarbonate block copolymers are characterized in that they are in the polymer chain on the one hand aromatic carbonate structural units (1) and on the other hand polydiorgano containing aryloxy end groups contain siloxanes (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, but 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 (I) is, for example, C ₁ -C ₂₀ -alkyl, alkenyl in the above formula (I) 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, alkenyls, aryls, halogenated Alkyls and halogenated aryls are methyl, ethyl, Propyl, n-butyl, tert-butyl, vinyl, phenyl, naphthyl, Chloromethyl, perfluorobutyl, perfluorooctyl and chlorine phenyl.

Such polydiorganosiloxane-polycarbonate block copoly mere are z. B. from U.S. Patent 3,189,662, U.S. Patent 3,821,325 and U.S. Patent 3,832,419 known.

Preferred polydiorganosiloxane polycarbonate block co polymers are made by using α, ω-bishydroxy aryloxy end group-containing polydiorganosiloxanes with other diphenols, if necessary with co-use chain terminators in the usual quantities and if necessary with the use of branches in the usual amounts, e.g. B. after the two-phase limit surface method (see H. Schnell, Chemistry and Physics of Polycarbonates Polymer Rev. Vol. IX, Pp. 27 ff, Interscience Publishers New York 1964) sets, the ratio of the bifunctional phenolic reactants is chosen so that the aromatic carbonate structure content according to the invention tur units and diorganosiloxy units results.  

Such a, ω-bishydroxyaryloxy end group-containing poly diorganosiloxanes are e.g. B. is known from US 3,419,634.

The rubber-elastic polymers C comprise copolymers - in particular graft copolymers - with rubber-elastic properties which are essentially obtainable 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 like them, e.g. B. in "Methods of Organic Chemistry" (Houben-Weyl), Vol. 14/1, Georg-Thieme-Verlag, Stuttgart 1961, pp. 393-406 and in CB Bucknall, "Toughened Plastics", Appl. Science Publishers, London 1977. The polymers C have a gel content of more than 20, preferably more than 40,% by weight. The glass transition temperature (Tg) is below -20 ° C.

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

In general, suitable for the preparation X-Y block copolymers made from styrene, α-methylstyrene, Vinyl toluene, etc. and from conjugated dienes, such as Butadiene, isoprene, etc., which are used in the manufacture of  Technology used styrene-diene block copolymers used in "Encyclopedia of Polymer Science and Technology ", Vol. 15, Interscience, N.Y. (1971) pages 508 ff. The selective hydry tion can be carried out in ways known per se become and means that the ethylenischen Doppelbin essentially completely hydrogenated, the aromatic double bonds essentially remain unaffected.

Such selectively hydrogenated block copolymers are e.g. B. described in DE-OS 30 00 282.

Preferred polymers C are e.g. B. with styrene and / or Acrylonitrile and / or (meth) acrylic acid alkyl esters grafted polybutadienes, butadiene / styrene copolymers and poly (meth) acrylic acid esters, e.g. B. copolymers Styrene or alkylstyrene and conjugated dienes (impact solid polystyrene), d. H. Copolymers of DE-OS 16 94 173 (= US-PS 3 564 077) described type, with Acrylic or methacrylic acid esters, vinyl acetate, acrylic Nitrile, styrene and / or alkylstyrenes grafted poly butadiene, butadiene / styrene or butadiene / acrylonitrile Copolymers, polyisobutenes or polyisoprenes, such as them e.g. B. in DE-OS 23 48 377 (= US-PS 3 919 353) or in DE-A-31 05 364 and DE-A-30 19 233 are described.

Particularly preferred polymers C are e.g. B. ABS poly merisate (both mixed and graft types) like them e.g. B. in DE-OS 20 35 390 (= US-PS 3 644 574) or in DE-OS 22 48 242 (= GB-PS 1 409 275) described are.  

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

• I. 10 to 40, preferably 10 to 35 wt .-% based on the graft product, 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 wt .-% based on graft product, a 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 μm, preferably 0.3 to 0, 5 µm (see, for example, EP 0 131 202).

(Meth) acrylic acid esters I are esters of acrylic acid or Methacrylic acid and monohydric alcohols with 1 to 8 C- Atoms.

In addition to butadiene residues, the graft base II can contain up to 30 wt .-% based on II, residues of other ethylenically unsaturated monomers such as e.g. B. styrene, acrylonitrile,  Esters of acrylic or methacrylic acid with 1 to 4 C- Atoms in the alcohol component (such as methyl acrylate, Ethyl acrylate, methyl methacrylate, ethyl methacrylate) ent hold. The preferred graft base II consists of pure polybutadiene.

Since the graft monomers I are known in the grafting reaction not completely based on the graft base II graft, according to the invention under graft polymers also understood such products that, in addition to the actual graft polymers also homo- and copoly contain merisate of the graft monomers I used.

The degree of grafting G denotes the weight ratio of to grafted graft monomers to 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 ultra-centrifuge measurements (W. Scholtan, X. Lange, Xolloid, 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 scattering measurements.

Particularly preferred polymers C are e.g. Belly 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 wt .-% based on C, at least one polymerizable, ethylenically unsaturated Monomers whose or in the absence of (a) resulting homo- or copolymers a glass transition temperature of 25 ° C as a graft monomers.

The acrylate rubbers (a) of the polymers C are preferably polymers of acrylic acid alkyl esters, optionally with up to 40% by weight of other polymerizable, ethylenically unsaturated monomers. If the acrylate rubbers used as the graft base (a) - as described below - are themselves graft products with a diene rubber core, 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 ver networks, preferably partially networked.  

Monomers with more than one poly copolymerizable double bond. Be preferred examples of crosslinking monomers are esters unsaturated monocarboxylic acids with 3 to 8 carbon atoms and saturated monohydric alcohols with 3 to 12 carbon atoms or saturated polyols with 2 to 4 OH groups and 2 up to 20 carbon atoms, such as B. ethylene glycol dimethacrylate, Allyl methacrylate, polyunsaturated heterocyclic Connections such as B. trivinyl and triallyl cyanurate and isocyanurate, tris-acryloyl-s-triazines, in particular Triallyl cyanurate; polyfunctional vinyl compounds such as Di- and trivinylbenzenes; but also triallyl phosphate and Diallyl phthalate.

Preferred crosslinking monomers are allyl methacrylate, Ethylene glycol dimethacrylate, diallyl phthalate and hetero cyclic compounds that are at least 3 ethylenic have unsaturated groups.

Particularly preferred crosslinking monomers are cyclic monomers triallyl cyanurate, triallyliso cyanurate, trivinyl cyanurate, triacryloylhexahydros triazine, triallylbenzenes.

The amount of crosslinking monomers is preferred as 0.02 to 5, in particular 0.05 to 2 wt .-% based on a graft basis (a).

In the case of cyclic crosslinking monomers with at least 3 ethylenically unsaturated groups it is advantageous the amount to be <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-methyl styrene, acrylamides, vinyl C ₁ -C ₆ alkyl ethers. 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 in at 25 ° C Dimethylformamide determined (M. Hoffmann, H. Krömer, R. Kuhn, Polymer Analytics I and II, Georg Thieme Verlag, Stuttgart 1977).

Acrylic rubbers as graft base (a) can also Products that are made of a cross-linked diene rubber one or more conjugated dienes, such as poly butadiene, or a copolymer of a conjugated Diene with an ethylenically unsaturated monomer such as Styrene and / or acrylonitrile, as the core.

The proportion of the polydiene core in the graft base (a) can 0.1 to 80, preferably 10 to 50 wt .-% based on (a). Shell and core can be independent of one another other be uncross-linked, partially cross-linked or highly cross-linked.

The aforementioned are very particularly preferred Graft polymers made from polybutadiene as a graft base and (meth) acrylic acid ester and acrylonitrile as a graft basis, the grafting base consisting of 65 to 90 parts by weight cross-linked polybutadiene with a gel content of  over 70% (in toluene) and the graft base from one 5: 1 to 20: 1 mixture of methyl methacrylate and n-butyl consist of acrylate (e.g. DE 31 05 364, DE 30 19 233).

Phosphite compounds (component D) in the sense of the invention are compounds 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 is a C ₁ -C ₁₈ monoalcohol radical containing oxetanyl groups,
Ar a radical of formula (II)

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 , 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 sense of the invention are compounds of the formula (III)

wherein
R ⁷ and R ^{8 are} identical 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, where R ^{9 represents} hydrogen, C ₁ -C ₆ alkyl or C ₅ -C ₆ cyclohexyl.

As alkyl radicals of the formulas (I), (II) and (III) come for example in question: methyl, ethyl, propyl, Isononyl, as aralkyl residues:

as cycloalkyl radicals: cyclopentyl, cyclohexyl,
as aryl residues: 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) are particularly preferred Formula (I) in which n = 0 means Ar for

stands, phosphoric acid (1-methyl ethylene) di-4,1-phenylene tetrakis (3-ethyl- (3-ox ethanyl) methyl) esters.  

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-methylbenzyl, 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 formula (I) can be in known by implementing appropriate Phosphites with diphenols (which differ from formula (II) lead) are produced (see. DE 25 10 463).

The phosphorous acid esters of the formula (III) can be in are known by the implementation of Triphenyl phosphite with the corresponding dihydroxyverbin dung in the presence of water (see e.g. DE 29 29 229).

The molding compositions can nucleating agents such as divided soot and microtalk included. Can continue  the molding compounds usual additives such as lubricant and Ent molding agents, fillers and reinforcing materials as well as paints contain substances and pigments (see component F).

The nucleating agents and additives can be used in amounts of about 0.1 to 1.0 parts by weight of the mold according to the invention masses are added.

Refurbished thermoplastic components Molding compositions of appropriate composition in the sense of Invention are components according to A), B) and / or C) such as described above. These components come from e.g. B. from Shaped bodies that do not come off with other thermoplastics mixed polycarbonate, polybutylene terephthalate or Graft polymer are produced. Before using them these components must be of one in their original state adhesive coating are exempted. This coating can e.g. B. a layer of paint, a metal layer, a paint layer, but also a combination of these layers be how to z. B. on a compact disc from the Areas of entertainment, communication and Data storage technology takes place. The release of the cover can be done according to different methods. So is it is possible to apply the coatings mechanically as well as chemically to remove. Chemical removal is suitable different methods, particularly suitable one Process in which the components are mixed with acids and / or Alkali and / or solvents are treated.

The method described in the European Application No. 476 475 is described in which Acids are used.  

It is a process for cleaning Wastes from thermoplastic, aromatic polycarbo naten and / or thermoplastic aromatic poly ester carbonates used in the manufacture of optical form parts such as audio compact discs, lenses for glasses or for other optical applications, or Lamp or headlight reflectors are required.

The process is characterized in particular by that the polycondensate waste by means of a shredder or a mill as described in the literature (see for example "Ullmanns Encyklopadie der technical chemistry, 4th edition (1972), volume 2 ver driving technique I (basic operations), SS 2-34 "), zer be reduced with acid to reflux with stirring be heated with water in a gentle manner Stir washed neutral that the polycon lacquer separated but not yet dissolved parts are rinsed out of the polycondensate Polycondensate after filtering off the water in the usual drying equipment, such as in "Ullmanns Encyclopedia of Chemical Engineering, 4th on lage (1972), volume 2, process engineering I (basic opera tion), SS 699 to 721 "are dried and, if necessary, then by wind sighting Apparatus such as that described in "Ullmanns Encyclopedia of Technical Chemistry, 4th edition (1972), Volume 2, Process Engineering I (Basic Operations), SS 57 to 69 are described, if necessary from the remaining paint residues or dye residues separated  become. In all cases where the polycondensate waste naturally does not contain metals these separately, for example as a powder before the acid added, optionally also in the form of metal salt.

It is particularly a method for cleaning Ab cases made of thermoplastic, aromatic polycarbonate ten and / or thermoplastic, aromatic polyester carbonates, the metals - optionally in the form of Metal salts -, lacquers and possibly dyes included, 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, zer shreds, then these fragments with acid at reflux heated with stirring, then with water with stirring neutral washes and finally with water for so long rinses until all of the paint separated from the polycondensate parts are rinsed out, the fragments are filtered off, dries and, if necessary, by air sifting paint and / or paint adhering to the fragments separates the remnants of the fabric.

By treating the polycondensate waste with acid after dissolving the metal, most of it will varnishes separated from polycarbonates and even partially dissolved.

Without the presence of a metal such as This effect does not occur with aluminum, since without aluminum nium reactive species such as nascent hydrogen and  Aluminum (III) salts are not formed "in situ" can.

Metals suitable for the cleaning process are excluded Aluminum, iron, zinc and tin. Iron, zinc and However, tin acts in a weakened form in comparison to aluminum.

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

Suitable dyes for the cleaning process are at for example those based on naphthaquinones, Benzoquinones, anthraquinones and azo compounds, as well organic pigments and inorganic pigments such as iron oxides, chromium oxides and titanium dioxide.

Polyalkylene terephthalates, such as. B. Polybutylene tere Phthalate is worked up mechanically, since it chemical reprocessing methods of decomposition tend.  

In particular, there is a method for cleaning Wastes from thermoplastic, aromatic polycar bonaten and / or thermoplastic, aromatic poly ester carbonates, the metals - optionally in the form of metal salts, paints and, if necessary, dyes included as a surface coating, the result is characterized that if necessary the Waste into fragments with an average diameter of 0.1 to 5.0 cm, preferably from 0.4 to 1.5 cm nert, these fragments afterwards in an all-round Particle radiation is subjected, whereby the adherent tendency surface coatings are removed.

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

That from the jet particles and the particles of the upper Surface coating formed mixture is then ßend separated and carried out in such a way that none Residues the quality of the pure thermo thus obtained plastic, aromatic polycarbonate and / or thermo plastic, aromatic polyester carbonate at the Disrupt further processing.

The processes are state of the art (DE-OS 15 77 537, US-P 3,392,491 and DE-OS 23 38 994).

The recycled components of the thermoplastic molding compounds corresponding composition in the sense of the invention in the original state, i.e. H. before the Reprocessing as moldings in various Applications have been used. So you can z. B.  in the automotive sector as a bumper or exterior mirror, or else have been used in the electronics sector as compact discs his.

The molding compositions according to the invention can be produced in the usual mixing units such as rollers, kneaders, Single or multi-shaft extruders by mixing the single individual components can be obtained.

Surprisingly, the examples show that only the mixtures have good properties where the reprocessed thermoplastic molding compounds ent speaking composition were used according to the procedures described were reprocessed. See examples 1 and 2.

It is particularly surprising that when you get one again refurbished component that is made of poly carbonate, which is usually found in compact dics is used, in addition to the expected ver improved flowability an unexpected good toughness.

Examples Component A:

Polybutylene terephthalate (PBT), intrinsic viscosity I.V. = 1.19 ± 0.03

Component B B.1 comparison

Linear polycarbonate based on bisphenol A, relative solution viscosity 1.20 ± 0.02 (see examples 1 and 2).

B.2 PC recyclate (according to the invention)

Linear polycarbonate based on bisphenol A, relative solution viscosity 1.20 ± 0.02

B.3 PC shredder (comparison)

PC shredder consists of shredded, untreated ten compact discs (average particle diameter approx. 0.8 mm), whose carrier material is made of linear Bisphenol A based polycarbonate, relative Solution viscosity 1.20 ± 0.02, and that still exists are painted and printed.  

Component C C.1 Rubber 1

Graft base of 75% polybutadiene and 25% a copolymer of 28% acrylonitrile and 72% Styrene, the mean particle diameter being the graft base in latex form between 0.3 and 0.5 µm.

C.2 Rubber 2

Graft copolymer, an emulsion polymer 80 parts by weight of crosslinked polybutadiene (gel content over 70%, measured in toluene) and 20 parts by weight Graft pad made from 18 parts by weight of methyl methacrylate and 2 parts by weight of n-butyl acrylate, the average particle diameter of latex present graft base between 0.3 and 0.5 µm (see information in DE-OS 31 05 364 and DE-OS 30 19 233).  

example 1 Composition of the molding compounds used

All examples contain common nucleating agents, Pigments and mold release agents (approx. 0.1% by weight).

Results

Example 2 Composition of the molding compounds used

All examples contain common nucleating agents, Pigments and mold release agents.

Results

Claims (8)

1. Thermoplastic molding compositions based on

• A) 1 to 99 parts by weight of polyalkylene terephthalate,
• B) 0 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 (Tg) of below -20 ° C.

and or

• D) 0.01 to 0.5 part by weight of a phosphite compound of the formula 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 is a C ₁ -C ₁₈ monoalcohol radical containing ent 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 cyclo are alkyl, 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 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 ₁₉ aryl
  and
  X represents -S- or R ⁹ -CH, where R ^{9 represents} 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) 5 to 80 parts by weight of a reprocessed thermoplastic component not mixed with other thermoplastics according to A), B) and / or C) are used in the molding composition from A) to F), components A) to G ) (A + B + C + D + E + F + G) add to 100.

2. Thermoplastic molding compositions according to claim 1, characterized in that

• A) 20 to 80 parts by weight of polyalkylene terephthalate,
• B) optionally 10 to 60 parts by weight of aromatic polycarbonate,
• C) 1 to 25 parts by weight of rubber-elastic polymer with a glass transition temperature (Tg) of below -20 ° C and / or
• D) 0.05 to 0.4 parts by weight of phosphite compound and / or
• E) 0.05 to 0.4 parts by weight of phosphoric acid ester and
• F) 0.1 to 1 part by weight of nucleating agents, pigments and / or mold release agents and
• G) 5 to 50 parts by weight of a reprocessed component

are included. 3. Molding composition according to claim 1, characterized in that component G) mechanically and / or chemically is worked up. 4. Use of remanufactured components according to component G of claim 1 for the preparation of molding compositions, characterized in that 5 to 80 parts by weight of the molding compositions from A + B + C + D + E + F according to Claim 1 from remanufactured components consist.   5. Shaped body, made from molding compositions according to Claim 1.