Polycarbonate composition with good stability

Abstract

The invention relates to a composition containing A) aromatic polycarbonate and / or polyester carbonate, in each case containing structural units derived from bisphenol A, B) rubber-modified vinyl (co)polymer, and C) a sulfonic acid and / or a sulfonic acid anhydride, wherein component C is used in an amount ranging from 0.0015 to 0.02 parts by weight, based on the sum of 100 parts by weight of components A and B. The invention also relates to a method for producing a molding compound from the composition, to the molding compound, to a molded body produced from the molding compound, and to the use of the aforementioned amount of sulfonic acid and / or sulfonic acid anhydride in order to reduce the content of free bisphenol A in a molding compound produced from the aforementioned components A and B and / or in order to reduce the content of free bisphenol A in a molded part obtained from such a molding compound.

Description

[0001] 2024PF30156 - Abroad

[0002] - 1 - Polycarbonate composition with good stability

[0003] The present invention relates to a polycarbonate and / or polyester carbonate composition, wherein the polycarbonate and / or polyester carbonate contains structural units derived from bisphenol A, further comprising rubber-modified vinyl (co)polymer and a sulfonic acid and / or a sulfonic anhydride, a process for producing a thermoplastic molding compound (hereinafter also referred to simply as "molding compound") from the composition, the molding compound itself, a molded part produced from the molding compound, and the use of a specific amount of a sulfonic acid and / or a sulfonic anhydride to reduce the content of free bisphenol A in a molding compound produced from the aforementioned polycarbonate and / or polyester carbonate and the aforementioned rubber-modified vinyl (co)polymer or to reduce the content of free bisphenol A in a molded part obtained from such a molding compound.

[0004] Polycarbonate and polyester carbonate compositions have been known for a long time, and these materials are used to manufacture molded parts for a wide variety of applications, for example in the automotive sector, for rail vehicles, for the construction sector, in the electrical / electronics sector, and for household appliances. It is also known that additives, fillers, and polymer blend partners can be added as further components of the composition to tailor the property profile to specific requirements. In many cases, rubber-based graft polymers are used as impact modifiers, particularly to increase toughness at low temperatures.

[0005] The production of molding compounds and molded parts from such compositions generally takes place at elevated temperatures, resulting in thermal stress on the compounds. Additionally, components of the molding compounds besides polycarbonate and / or polyester carbonates, particularly process-related impurities in the rubber-based graft polymers, can, under this thermal stress and the simultaneous influence of residual moisture that cannot be completely avoided during the process, lead to undesirable degradation of the polymer chains of the polycarbonate or polyester carbonate. This degradation ultimately results in impaired mechanical properties of the molded parts produced from these compositions.

[0006] The stabilization of polycarbonate compositions is therefore of great importance and is described in numerous documents. For example, WO 2007 / 065579 Al2024PF30156-Ausland discloses

[0007] - 2 - Polycarbonate compositions containing graft polymer, stabilized by the addition of an organic carboxylic acid. DE 197 53 542 Al discloses molding compounds containing polycarbonate, graft polymer and filler as well as a low molecular weight acid, such as p-toluenesulfonic acid, in an amount of 0.05 to 2% by weight, based on the total composition.

[0008] In the case of polycarbonate and / or polyester carbonate containing bisphenol A (BPA) as a structural component, degradation reactions can eventually lead to the formation of free, i.e., unbound, BPA in the molding compounds and molded bodies in elevated concentrations.

[0009] In the European Union, with the aim of reducing the release of BPA into the aquatic environment, a restriction under the REACH Regulation for BPA in polycarbonate-containing mixtures, i.e., in compositions and molding compounds, and in polycarbonate-containing articles, i.e., molded bodies, is currently being discussed. Most recently, a limit of 150 mg / kg (ppm) for free BPA in mixtures and articles was proposed as a prerequisite for future marketing.

[0010] The reduction of free bisphenol A is therefore also the goal of many prior art studies.

[0011] WO 2013 / 160371 Al discloses PC / ABS compositions, in particular those based on ABS produced by emulsion polymerization process, wherein the compositions are characterized by a low content of free bisphenol A.

[0012] WO 2013 / 160373 discloses PC / ABS compositions containing polycarbonate with low OH end group content (preferably produced by interfacial polymerization) and ABS with low alkali content (preferably produced by bulk polymerization), which are characterized by high thermal processing stability with respect to gloss level, polycarbonate degradation and free bisphenol A content and exhibit improved stress crack resistance.

[0013] WO 2019 / 121463 discloses a composition for producing a thermoplastic molding compound and injection-molded parts therefrom with a reduced content of free bisphenol A, comprising an aromatic polycarbonate with a phenolic OH end group content of at least 200 mg / kg as component A, a rubber-based graft polymer as component B, and an ester of a sulfonic acid as component C. 2024PF30156-Abroad

[0014] - 3 - The document further discloses that, in particular, thermoplastic molding compounds and injection-molded bodies produced from them from compositions containing aromatic polycarbonate produced by melt polymerization and ABS produced by bulk polymerization may have a high content of free BPA.

[0015] The latter document also states that the addition of additives, especially acids, as thermostabilizers carries the risk that while thermal stability may be improved, other properties such as resistance to warm, humid conditions (i.e., resistance to hydrolytic polymer degradation) may be impaired.

[0016] In addition to hydrolysis stability, the addition of thermal stabilizers is also noteworthy because, in many cases, it has an undesirable effect on the inherent color of the molding compounds and the resulting molded parts, manifesting as an increase in the yellowness index. This adverse effect increases with increasing thermal exposure during compounding or injection molding; that is, it is particularly pronounced when processed at high melt temperatures and / or with long residence times. Therefore, when using stabilizers known from the prior art, which are capable of reducing polycarbonate release and thus the formation of free BPA during processing, effective concentrations of these additives result in an undesirably restricted processing window for the molding compounds.This, among other undesirable effects, limits the melt flowability of the molding compounds and thus their suitability for the production of complex, especially large-area and thin-walled components.

[0017] In view of the aforementioned regulatory efforts, the reductions in the content of free bisphenol A achieved so far are not yet sufficient, especially when the composition contains polycarbonate produced by melt polymerization and ABS produced by bulk polymerization.

[0018] It was therefore desirable to provide BPA-stabilized polycarbonate and / or BPA-polyester carbonate compositions containing rubber-modified vinyl (co)polymer, which are stabilized against BPA release during melt compounding and melt processing, and from which molding compounds and molded parts with a reduced content of free bisphenol A (reliably less than 150 ppm within the expected production fluctuations and analytical measurement errors) can be produced. In particular, it was desirable that the free BPA content remain at this low level even when polycarbonate and / or polyester carbonate are produced by melt polymerization and exported as 2024PF30156-Abroad

[0019] - 4 - Rubber-modified vinyl(co)polymer, an ABS produced using a bulk polymerization process, is used. Furthermore, it was desirable that the molding compounds exhibit low hydrolysis sensitivity and that molded parts produced from such compounds (without the use of counteracting colorants in the molding compounds) also exhibit a low yellow value, even when using high melting temperatures and long residence times during molding. The goal was therefore to achieve a combination of low BPA values ​​in the molding compounds and the molded parts produced from them, good hydrolysis stability of the molding compounds, and a low yellow value in the molded parts produced from them.

[0020] To achieve a free bisphenol A (BPA) content in the molding compounds and molded parts according to the invention that is statistically reliably less than 150 ppm within the expected production fluctuations and analytical measurement errors, a BPA content of <100 ppm in the molding compound and the resulting molded part was targeted within the scope of this invention. To reliably achieve a free BPA content of less than 150 ppm in the molded parts even under unfavorable conditions (e.g., high melt temperatures, long residence times of the melt in the screw conveyor, insufficient drying, i.e., high residual moisture) during injection molding, free BPA levels of <50 ppm were preferably targeted in the molding compounds prior to injection molding.

[0021] It has now been surprisingly found that the composition contains

[0022] A) an aromatic polycarbonate and / or polyester carbonate, each containing structural units derived from bisphenol A,

[0023] B) rubber-modified vinyl(co)polymer,

[0024] C) a sulfonic acid and / or a sulfonic anhydride,

[0025] where component C is used in an amount of 0.0015 to 0.02 parts by weight (2-200 ppm), based on a total of 100 parts by weight of components A and B,

[0026] which has advantageous properties.

[0027] In a preferred embodiment, the quantity of component C is 0.0015 to 0.015 parts by weight, more preferably 0.0015 to 0.008 parts by weight, and particularly preferably 0.002 to 0.006 parts by weight. When component C is used in these preferred quantities, then 2024PF30156-Abroad

[0028] - 5 -particularly low levels of free bisphenol A can be achieved with good hydrolysis stability and acceptable yellow values.

[0029] Containing structural units “derived from a bisphenol A” in the context of this invention means that bisphenol A is used in the manufacture of component A. The bisphenol A is then covalently incorporated into the polymer chain of component A, unless it is released again through undesired degradation reactions.

[0030] The composition preferably contains 30 to 95 parts by weight of component A and 5 to 70 parts by weight of component B, more preferably 40 to 80 parts by weight of component A and 20 to 60 parts by weight of component B, and particularly preferably 50 to 75 parts by weight of component A and 25 to 50 parts by weight of component B, wherein all parts by weight are based on a total of 100 parts by weight of components A and B.

[0031] The composition may optionally include at least one polymer additive different from component C and / or a polymeric component different from components A and B as component D.

[0032] Component D is preferably used in a total proportion of 0 to 40 parts by weight, more preferably 0.01 to 40 parts by weight, more preferably 0.05 to 20 parts by weight, particularly preferably 0.1 to 10 parts by weight and most preferably 0.2 to 2 parts by weight, each based on a total of 100 parts by weight of components A and B.

[0033] In a preferred embodiment, the composition consists of at least 90 wt.%, particularly preferably at least 95 wt.%, and most preferably at least 98 wt.% of components A to D. In a further preferred embodiment, the composition consists only of components A to D.

[0034] In a preferred embodiment, the composition contains > 0.5 ppm, more preferably > 1 ppm lithium, in each case to be understood as weight fractions.

[0035] The term “a polycarbonate and / or polyester carbonate” for component A also includes mixtures of different polycarbonates, mixtures of different polyester carbonates, and mixtures of one or more polycarbonates with one or more polyester carbonates. “A polycarbonate and / or polyester carbonate” is therefore to be understood as “at least one polycarbonate and / or at least one polyester carbonate.” This applies analogously to the other components B, C, and D contained in the composition according to the invention and their monomer Z structural building blocks. 2024PF30156-Abroad

[0036] - 6 -

[0037] Another task was to provide a process for producing a molding compound from a composition containing polycarbonate and / or polyester carbonate, each containing structural units derived from bisphenol A, and containing rubber-modified vinyl (co)polymer, wherein the molding compound has a low content of free BPA and is suitable for producing molded bodies with a similarly low content of free BPA using injection molding and within a wide processing window, wherein the molding compound preferably also has good hydrolysis resistance and the molded bodies obtained from it preferably also have a low yellowing value even under high thermal stress during molding.

[0038] It was particularly desirable that the desired properties be achieved in this process when at least partially a polycarbonate and / or polyester carbonate produced by melt polymerization process and a rubber-modified vinyl(co)polymer produced by bulk polymerization process are used.

[0039] It has now been found that a process for producing a thermoplastic molding compound containing

[0040] A) an aromatic polycarbonate and / or polyester carbonate, each containing structural units derived from bisphenol A and

[0041] B) rubber-modified vinyl(co)polymer,

[0042] the components are mixed together at a temperature of 200 to 350 °C and melted and dispersed into each other in a compounding unit,

[0043] characterized in that, in the process, a sulfonic acid and / or a sulfonic anhydride is added as component C) in an amount, based on a total of 100 parts by weight of components A and B, of 0.0015 to 0.02 parts by weight.

[0044] and wherein either the mixing of components A, B, C and optionally of component C different polymer additives and / or of components A and B different polymeric components as component D takes place in a single step or alternatively the component C is first premixed in a first step with the total amount or a subset of component A at room temperature or at an elevated temperature of preferably 200 to 350°C,2024PF30156-Abroad

[0045] - 7 - the desired improvements achieved.

[0046] A further object of the present invention is the use of 0.0015 to 0.02 parts by weight of a sulfonic acid and / or a sulfonic anhydride for reducing the content of free bisphenol A in a molding compound produced from a composition containing the above-mentioned components A and B and / or for reducing the content of free bisphenol A in a molded part obtained from such a molding compound, wherein the parts by weight of the sulfonic acid and / or the sulfonic anhydride relate to a total of 100 parts by weight of components A and B.

[0047] All preferred embodiments mentioned in this invention for the composition according to the invention also apply to the process and use according to the invention.

[0048] Component A

[0049] Component A is at least one representative selected from the group consisting of polycarbonate and polyester carbonate, each containing structural units derived from bisphenol A.

[0050] Suitable polycarbonates and / or polyester carbonates according to component A are known from the literature or can be produced using methods known from the literature (for the production of polycarbonates, see, for example, Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964, as well as DE-AS 1 495 626, DE-A 2232877, DE-A 2703 376, DE-A 2714544, DE-A 3 000610, DE-A 3 832396; for the production of polyester carbonates, see, for example, DE-A 3 007934).

[0051] The production of polycarbonates suitable as component A according to the invention is carried out, for example, by reacting bisphenol A and optionally further dihydroxyaryl compounds (also referred to as aromatic diols, diphenols or bisphenols) and / or aliphatic diols with carbonic acid halides, preferably phosgene and / or with aromatic dicarboxylic acid dihalides, preferably benzene dicarboxylic acid dihalides, by the interface process, optionally using chain terminators, for example monophenols and optionally using trifunctional or more than trifunctional branchers, for example trihydroxyaryl or tetrahydroxyaryl compounds. Likewise, production via a melt polymerization process by reacting bisphenol A and optionally further dihydroxyaryl compounds and / or aliphatic diols with carbonic acid halides is also possible.

[0052] - 8 - for example, diphenyl carbonate is possible. Production via a melt polymerization process is preferred.

[0053] In addition to bisphenol A for the production of the polycarbonates suitable as component A according to the invention and / or for the production of the polyester carbonates suitable as component A according to the invention, dihydroxyaryl compounds of formula (1) are preferably used.

[0054]

[0055] (1)

[0056] where

[0057] A CI to C5 alkylenes, C2 to C5 alkylidenes, C5 to C6 cycloalkylidenes, C6 to C12 arylenes, to which further aromatic rings, possibly containing heteroatoms, may be fused, a single bond, -O-, -SO-, -CO-, -S-, -SO2-,

[0058] or a remainder of formula (2) or (3)

[0059]

[0060] (3)

[0061] B each Ci to Cn alkyl, preferably methyl, halogen, preferably chlorine and / or bromine

[0062] x each independently 0, 1 or 2,

[0063] p 1 or 0 are, and 2024PF30156-abroad

[0064] - 9 - R 5 and R 6 for each X 1 individually selectable, independently of each other hydrogen or Ci to Ce-alkyl, preferably hydrogen, methyl or ethyl,

[0065] XI Carbon and

[0066] m can be an integer from 4 to 7, preferably 4 or 5, with the proviso that at least one atom X 1 , R 5 and R 6 are simultaneously alkyl.

[0067] In the context of the present invention, the term “alkylene” or “alkylene group” preferably refers, unless otherwise specified, to a bridging alkane structure from which two hydrogen atoms have been removed from different carbon atoms.

[0068] In the context of the present invention, the term “alkylidene” or “alkylidene group” preferably refers, unless otherwise specified, to a bridging alkane structure in which two hydrogen atoms have been removed from the same carbon atom.

[0069] Preferred dihydroxyaryl compounds used alongside bisphenol A are hydroquinone, resorcinol, dihydroxydiphenyls, bis-(hydroxyphenyl)alkanes, bis-(hydroxyphenyl)cycloalkanes, bis-(hydroxyphenyl)sulfides, bis-(hydroxyphenyl) ethers, bis-(hydroxyphenyl)ketones, bis-(hydroxyphenyl)sulfones, bis-(hydroxyphenyl)sulfoxides, α-α'-bis-(hydroxyphenyl)diisopropylbenzenes, phthalimidines derived from isatin or phenolphthalein derivatives, and their kemalkylated, kemarylated, and kemhalogenated compounds.

[0070] Other preferred dihydroxyaryl compounds used alongside bisphenol A include 4,4'-dihydroxydiphenyl, 2,4-bis-(4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(4-hydroxyphenyl)-p-diisopropylbenzene, 2,2-bis-(3-methyl-4-hydroxyphenyl)-propane, dimethyl bisphenol A, bis-(3,5-dimethyl-4-hydroxyphenyl)-methane, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, bis-(3,5-dimethyl-4-hydroxyphenyl)-sulfone, 2,4-bis-(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(3,5-dimethyl-4-hydroxyphenyl)-p-diisopropylbenzene, and 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane. Dihydroxyaryl compounds (I) to (III)2024PF30156-Foreign

[0071] - 10 -

[0072]

[0073] These and other suitable dihydroxyaryl compounds are, for example, in US 3 028 635 A, US 2 999 835 A, US 3 148 172 A, US 2 991 273 A, US 3 271 367 A, US 4 982 014 A and US 2 999 846 A, in DE 1 570 703 A, DE 2063 050 A, DE 2 036052 A, DE 2211 956 A and DE 3 832 396 A, in FR 1 561 518 A, in the monograph "H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964" as well as in JP 62039 / 1986 A, JP 62040 / 1986 A and JP 105550 / 1986 A described.

[0074] These dihydroxyaryl compounds can be used individually or in any mixture. The dihydroxyaryl compounds are known from the literature or can be obtained by methods known from the literature.

[0075] The polycarbonates used according to the invention preferably contain at least 20 wt.%, more preferably at least 50 wt.%, particularly preferably at least 80 wt.%, most preferably 100 wt.%, in each case based on the sum of all structural units derived from dihydroxyaryl compounds, such as those derived from bisphenol A.

[0076] Suitable aliphatic diols are selected from the group consisting of 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2-bis(4-hydroxycyclohexyl)propane, tetrahydro-2,5-furandimethanol, 2-butyl-2-ethyl-1,3-propanediol, 2-(2-hydroxyethoxyethanol), 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,2-dimethylpropane-1,3-diol, cyclobutane-1,1-diyldimethanol, 8-(hydroxymethyl)-3 -tricyclo[5.2.1.02,6]decanyl]methanol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, isosorbide and any mixtures thereof.

[0077] The polycarbonates used according to the invention preferably contain at least 20 wt.%, more preferably at least 50 wt.%, particularly preferably at least 80 wt.%, most preferably 100 wt.%, in each case based on the sum of all structural units derived from dihydroxyaryl compounds and aliphatic diols, such as those derived from bisphenol A. 2024PF30156-Abroad

[0078] - 11 - Suitable chain terminations for the production of polycarbonates include, for example, phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, but also long-chain alkylphenols, such as 4-[2-(2,4,4-trimethylpentyl)]phenol, 4-(1,3-tetramethylbutyl)phenol according to DE-A 2 842 005 or monoalkylphenol or dialkylphenols with a total of 8 to 20 carbon atoms in the alkyl substituents, such as 3,5-di-tert-butylphenol, p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol and 2-(3,5-dimethylheptyl)phenol and 4-(3,5-dimethylheptyl)phenol. The amount of chain terminators to be used is generally between 0.5 mol% and 10 mol%, based on the total molar content of the dihydroxyaryl compounds used.

[0079] The thermoplastic aromatic polycarbonates have medium molecular weights (average weight M). w) preferably 15,000 to 50,000 g / mol, further preferably 20,000 to 35,000 g / mol, particularly preferably 24,000 to 32,000 g / mol, measured by GPC (gel permeation chromatography) using dichloromethane as the solvent and with calibration using linear polycarbonates (from bisphenol A and phosgene) of known molar mass distribution from PSS Polymer Standards Service GmbH, Germany, calibration according to method 2301-0257502-09D (from 2009 in German) of Currenta GmbH & Co. OHG, Leverkusen. The eluent is dichloromethane. Column combination made of cross-linked styrene-divinylbenzene resins. Diameter of the analytical columns: 7.5 mm; length: 300 mm. Particle sizes of the column material: 3 pm to 20 pm. Concentration of the solutions: 0.2 wt%. Flow rate: 1.0 ml / min, solution temperature: 30°C. Use of UV and / or RI detection.Due to the preferred molecular face regions of component A, a particularly advantageous balance of mechanical and rheological properties is achieved in the compositions according to the invention.

[0080] The polycarbonates can be branched in a known manner, preferably by the incorporation of 0.05 to 2.0 mol%, based on the total number of dihydroxyaryl compounds used, of trifunctional or more than trifunctional compounds, for example, those with three or more phenolic groups. Linear polycarbonates are preferred, and linear polycarbonates based exclusively on bisphenol A are even more preferred.

[0081] Both homopolycarbonates and copolycarbonates are suitable. For the production of copolycarbonates according to the invention, component A, 1 to 25 wt.%, preferably 2.5 to 25 wt.%, based on the total amount of dihydroxyaryl compounds to be used, of polydiorganosiloxanes with hydroxyaryloxy end groups can also be used. These are known (US 3,419,634) and according to methods known from the literature.

[0082] - 12 -producible. The production of the polydiorganosiloxane-containing copolycarbonates obtained in this way is described, for example, in DE-A 3 334 782 and W02015 / 052106 A2.

[0083] Copolycarbonates produced using diphenols of general formula (3a) are also preferred:

[0084]

[0085] (3a),

[0086] where

[0087] R 5for hydrogen or Ci- to C4-alkyl, Ci- to Cs-alkoxy, preferably for hydrogen; methoxy or methyl, stands,

[0088] R 6 , R 7 , R 8 and R 9 each independently of one another stand for Ci- to C4-alkyl or Ce- to Cn-aryl, preferably for methyl or phenyl,

[0089] Y represents a single bond, SO2-, -S-, -CO-, -O-, Ci- to Ce-alkylene, C2- to Ce-alkylidene, Ce- to Ci2-arylene, which may optionally be condensed with aromatic rings containing further heteroatoms, or a C5- to Ce-cycloalkylidene residue which may be substituted once or several times with Ci- to C4-alkyl, preferably a single bond, -O-, isopropylidene or a C5- to Ce-cycloalkylidene residue which may be substituted once or several times with Ci- to C4-alkyl.

[0090] V for oxygen, C2- to Ce-alkylenes or C3- to Ce-alkylidenes, preferably for oxygen or C3-alkylenes,

[0091] p, q and r each independently represent 0 or 1,

[0092] when q = 0, W represents a single bond; when q = 1 and r = 0, W represents oxygen, C2- to Ce-alkylenes or C3- to Ce-alkylidenes, preferably oxygen or Cs-alkylenes.

[0093] where q = 1 and r = 1, W and V each independently represent C2- to Ce-alkylenes or C3- to Ce-alkylidenes, preferably C3-alkylenes,

[0094] Z stands for a Ci- to Ce-alkylene, preferably Cs-alkylene, 2024PF30156-Abroad

[0095] - 13 - o stands for an average number of repetition units of 10 to 500, preferably 10 to 100, and

[0096] m represents an average number of repeating units of 1 to 10, preferably 1 to 6, more preferably 1.5 to 5. It is also possible to use diphenols in which two or more siloxane blocks of general formula (4a) are linked to one another via terephthalic acid and / or isophthalic acid to form ester groups.

[0097] Particularly preferred are (poly)siloxanes of formulas (4) and (5)

[0098]

[0099] where RI stands for hydrogen, Ci to C4 alkyl, preferably for hydrogen or methyl, and particularly preferably for hydrogen,

[0100] R2 independently for aryl or alkyl, preferably for methyl,

[0101] X stands for a single bond, -SO2-, -CO-, -O-, -S-, Ci- to Ce -alkylenes, C2- to Cs-alkylidenes or for Ce- to Cn-arylene, which may optionally be condensed with further aromatic rings containing heteroatoms,

[0102] X preferably represents a single bond, Ci- to Cs-alkylenes, C2- to Cs-alkylidenes, Cs- to C12-cycloalkylidenes, -O-, -SO-, -CO-, -S-, -SO2-, particularly preferably X represents a single bond, isopropylidenes, Cs- to Cn-cycloalkylidenes or oxygen, and most particularly preferably represents isopropylidenes.

[0103] n means an average number of 10 to 400, preferably 10 and 100, particularly preferably 15 to 50 and 2024PF30156-Abroad

[0104] - 14 -m stands for an average number of 1 to 10, preferably of 1 to 6 and particularly preferably of 1.5 to 5.

[0105] The siloxane block can also preferably be derived from the following structure.

[0106]

[0107] where a in formula (6), (7), (7a) and (8) represents an average number of 10 to 400, preferably 10 to 100 and most preferably 15 to 50.

[0108] It is also preferred that at least two identical or different siloxane blocks of the general formulas (6), (7), (7a) and (8) are linked together via terephthalic acid and / or isophthalic acid to form ester groups.

[0109] Likewise, it is preferred if in formula (4a) p = 0, V stands for Cs-alkylene, r = 1, Z stands for Cs-alkylene, R 8 and R 9 where q = 1 represents methyl, W represents Cs-alkylene, m = 1 represents R 5 R stands for hydrogen or Ci- to C4-alkyl, preferably for hydrogen or methyl. 6 and R 7 each independently of each other stands for Ci to C4 alkyl, preferably for methyl, and o stands for 10 to 500.

[0110] Copolycarbonates with monomer units of formula (3a) and in particular their preparation are described in WO 2015 / 052106 A2. Copolycarbonates with 2024PF30156-Abroad

[0111] - 15 - Monomer units of formula (6) and in particular their preparation are described in WO 2015 / 052106 A2.

[0112] Aromatic dicarboxylic acid dihalides for the production of polyester carbonates are preferably the diacid dichlorides of isophthalic acid, terephthalic acid, diphenyl ether-4,4'-dicarboxylic acid, and naphthalene-2,6-dicarboxylic acid. Mixtures of the diacid dichlorides of isophthalic acid and terephthalic acid in a ratio between 1:20 and 20:1 are particularly preferred. In the production of polyester carbonates, a carbonic acid halide, preferably phosgene, is additionally used as a bifunctional acid derivative.

[0113] In addition to the monophenols already mentioned, other suitable chain terminators for the production of polyester carbonates include their chlorocarbonate esters, the acid chlorides of aromatic monocarboxylic acids, which may optionally be substituted by Ci to C22 alkyl groups or by halogen atoms, and aliphatic C2 to C22 monocarboxylic acid chlorides.

[0114] The amount of chain terminators is 0.1 to 10 mol% in each case, based on moles of dihydroxyaryl compound in the case of phenolic chain terminators and on moles of dicarboxylic acid dichloride in the case of monocarboxylic acid chloride chain terminators.

[0115] In the production of polyester carbonates, one or more aromatic hydroxycarboxylic acids can also be used.

[0116] The polyester carbonates can be either linear or branched in a known manner (see DE-A 2 940 024 and DE-A 3 007 934), with linear polyester carbonates being preferred.

[0117] Branching agents can include, for example, tri- or multi-functional carboxylic acid chlorides, such as trimesic acid trichloride, cyanuric acid trichloride, 3,3'-,4,4'-benzophenone tetracarboxylic acid tetrachloride, 1,4,5,8-napthalin tetracarboxylic acid tetrachloride, or pyromellitic acid tetrachloride, in amounts of 0.01 to 1.0 mol% (based on the dicarboxylic acid dichlorides used), or tri- or multi-functional phenols, such as phloroglucinol, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)hept-2-ene, 4,6-dimethyl-2,4-6-tri-(4-hydroxyphenyl)heptane, 1,3,5-tri-(4-hydroxyphenyl)benzene, 1,1,1-tri-(4-hydroxyphenyl)ethane, tri-(4-hydroxyphenylj-phenylmethane), 2,2-bis[4, 4-bis(4-hydroxyphenyl)-cyclohexyl] propane, 2,4-bis(4-hydroxyphenyl-isopropyl)-phenol, tetra-(4-hydroxyphenyl)-methane, 2,6-bis(2-hydroxy-5-methyl-benzyl)-4-methyl-phenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propane, Tetra-(4-[4-hydroxyphenyl-isopropyl]-phenoxy)-methane, 1,4-bis[4,4'-dihydroxytri-phenyl)-methyl]-benzene, in amounts of 0.01 to 1,0 mol% based on the amount of 2024PF30156 used abroad,

[0118] - 16 - Dihydroxyaryl compounds may be used. Phenolic branching agents may be introduced with the dihydroxyaryl compounds; acid chloride branching agents may be introduced together with the acid dichlorides.

[0119] In polyester carbonates, the proportion of carbonate structural units can vary as desired. Preferably, the proportion of carbonate groups is up to 90 mol%, particularly up to 80 mol%, and most preferably up to 50 mol%, based on the sum of ester and carbonate groups. Both the ester and carbonate components of the polyester carbonates can be present in the form of blocks or statistically distributed within the polycondensate.

[0120] The polycarbonates and polyester carbonates can be used alone or in any mixture. Preferably, linear polycarbonate based exclusively on bisphenol A is used as component A.

[0121] In a special embodiment, the polycarbonates or polyester carbonates used as component A contain one or more structures of the general formulas (IV) to (VII), which are the result of Fries rearrangement reactions and which are referred to below as “Fries structures” or “rearrangement structures”, 2024PF30156-Abroad

[0122]

[0123] in which the phenyl rings can be independently substituted once or twice with Cl-C8 alkyl, halogen such as chlorine or bromine, preferably Cl-C4 alkyl, especially methyl, and A has the meaning given in formula (I),

[0124] In this particular embodiment, the total amount of structural units (IV) to (VII) is at least 50 mg / kg, based on the sum of aromatic polycarbonate and polyester carbonate according to component A. Preferably, the amount of structural units (IV) to (VII) is 50 to 10,000 mg / kg, particularly preferably 100 to 3,000 mg / kg, and most preferably 200 to 1,200 mg / kg, in each case based on the sum of aromatic polycarbonate and polyester carbonate according to component A.

[0125] The structural units of formulas (IV) to (VII) are derived from and result from the diphenols used in the production of the polycarbonate. For example, in the case of bisphenol A as the diphenol, the phenyl rings of the rearrangement structures are unsubstituted. 2024PF30156-Abroad

[0126] - 18 - In the degradation by alkaline saponification of the aromatic polycarbonates and / or aromatic polyester carbonates according to component A for analytical purposes, the low molecular weight degradation products characteristic of the respective rearrangement structures of formulas (IVa) to (Vila), shown as an example for bisphenol A as diphenol (i.e. for A = isopropylidene), are formed and their amounts are determined after separation by HPLC with nuclear magnetic resonance spectroscopy (¹H NMR).

[0127] (IVa)

[0128] OH

[0129] I

[0130] H

[0131] (Vlla)

[0132]

[0133] Aromatic polycarbonates and / or polyester carbonates containing such frieze structures are produced in a special form using the melt polymerization process.

[0134] In another embodiment, the aromatic polycarbonates and / or polyester carbonates used as component A have a phenolic content of OH-2024PF30156-Ausland

[0135] - 19 - End groups of preferably at least 200 mg / kg, further preferably at least 300 mg / kg, in particular at least 400 mg / kg.

[0136] The concentration of phenolic OH end groups in component A is determined by infrared spectroscopy according to Horbach, A.; Veiel, U.; Wunderlich, H., Macromolecular Chemistry, 1965, Volume 88, pp. 215-231.

[0137] In another embodiment, the aromatic polycarbonates and / or polyester carbonates used as component A have a content of phenolic OH end groups of preferably at least 100 mg / kg, particularly preferably at least 200 mg / kg, more preferably at least 300 mg / kg, and in particular at least 400 mg / kg, and contain one or more Fries structures of the general formulas (IV) to (VII).

[0138] Component B

[0139] Component B in the composition according to the invention is a rubber-modified vinyl(co)polymer.

[0140] The rubber-modified vinyl (co)polymer according to component B is a rubber-modified graft polymer or a mixture of a rubber-modified graft polymer and a rubber-free vinyl (co)polymer. The rubber-free vinyl (co)polymer in component B can be formed incidentally during the production of a rubber-modified graft polymer and / or added to component B as a separately produced polymer.

[0141] The rubber-modified vinyl(co)polymer preferably comprises

[0142] 5 to 95, preferably 15 to 93, in particular 20 to 92 wt.%, based on the rubber-modified vinyl(co)polymer, at least one vinyl(co)polymer and

[0143] 95 to 5, preferably 85 to 7, in particular 80 to 8 wt.%, based on the rubber-modified vinyl(co)polymer, of one or more rubbers, preferably with glass transition temperatures < 10°C, further preferably < 0°C, particularly preferably < -20°C.

[0144] In the rubber-modified vinyl (co)polymer, the vinyl(co)polymer is at least partially chemically bonded to the rubber (grafted onto the rubber) and optionally partially enclosed in the rubber particles in such a way that it does not escape from the compositions according to the invention during their manufacture and processing.

[0145] - 20 - emerges from rubber particles. In contrast to the so-called "free" vinyl (co)polymer fraction (corresponding to the "rubber-free vinyl (co)polymer"), both the chemically bonded (i.e., grafted) and the fraction enclosed (i.e., included) within the rubber particles are not extractable in solvents.

[0146] Unless otherwise expressly described in the present invention, the glass transition temperature is determined for all components by means of differential scanning calorimetry (DSC) according to DIN EN 61006 (version of 1994) at a heating rate of 10 K / min with determination of Tg as the midpoint temperature (tangent method).

[0147] The rubber particles generally have a mean particle size (dso value) of 0.05 to 10 pm, preferably 0.2 to 5 pm, particularly preferably 0.3 to 1.5 pm.

[0148] The mean particle size dso is the diameter above and below which 50 wt% of the particles lie. It can be determined by ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. and Z. Polymere 250 (1972), 782-1796).

[0149] The rubber-modified graft polymers and the separately prepared rubber-free vinyl (co)polymers, as (optional) components of the rubber-modified vinyl (co)polymer according to component B, are usually produced by methods known from the literature, such as radical polymerization, e.g., by emulsion, suspension, solution, or bulk polymerization. Component B can also consist of mixtures of rubber-modified graft polymers and rubber-free vinyl (co)polymers produced by different methods.

[0150] The rubber-modified graft polymer can, for example, have a Kem shell structure. Such rubber-modified graft polymers with a Kem shell structure are typically produced by emulsion polymerization and generally have a rubber content in the range of 20 to 90 wt.%, preferably 30 to 85 wt.%, more preferably 40 to 80 wt.%.

[0151] Preferably, the rubber-modified vinyl(co)polymers contained in component B are those which, due to the manufacturing process, contain a dispersed phase of rubber particles grafted with vinyl(co)polymer, including vinyl(co)polymer inclusions embedded in a vinyl(co)polymer matrix. Such rubber-modified graft polymers can be obtained by bulk polymerization. Component B particularly preferably contains at least 50 wt%, and more preferably at least 802024PF30156-Ausland

[0152] - 21 wt.%, particularly preferably at least 90 wt.% of such rubber-modified vinyl (co)polymers with the inclusions mentioned, preferably produced by bulk polymerization. Most preferably, component B consists of such rubber-modified vinyl (co)polymers.

[0153] Vinyl monomers for the production of rubber-modified and rubber-free vinyl (co)polymers are preferably mixtures of

[0154] 50 to 99, preferably 60 to 80, particularly 70 to 80 parts by weight, based on the vinyl(co)polymer in the rubber-modified and / or rubber-free vinyl(co)polymer, vinyl aromatics and / or keme-substituted vinyl aromatics (such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) and / or methacrylic acid (Ci-Cs) alkyl esters, such as methyl methacrylate, ethyl methacrylate), preferably selected from at least one of the monomers styrene, α-methylstyrene and methyl methacrylate, particularly preferably styrene and

[0155] 1 to 50, preferably 20 to 40, in particular 20 to 30 parts by weight, based on the vinyl(co)polymer in the rubber-modified and / or rubber-free vinyl(co)polymer, vinyl cyanides (unsaturated nitriles such as acrylonitrile and methacrylonitrile) and / or (meth)acrylic acid (Ci-Cs) alkyl esters, such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and / or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids, for example maleic anhydride and N-phenyl maleimide, preferably selected from at least one of the monomers acrylonitrile, maleic anhydride and methyl methacrylate, particularly preferably acrylonitrile.

[0156] In another preferred embodiment, the vinyl(co)polymer in component B is at least partially polymethyl ethacrylate.

[0157] Suitable rubbers for the rubber-modified graft polymers include, for example, diene rubbers, EP(D)M rubbers (i.e., those based on ethylene / propylene and, if applicable, diene), acrylate, polyurethane, silicone, chloroprene, and ethylene / vinyl acetate rubbers, as well as silicone / acrylate composite rubbers. Other suitable rubbers are silicone rubbers with graft-active sites, as described in DE-OS 3 704 657, DE-OS 3 704 655, DE-OS 3 631 540, and DE-OS 3 631 539. 2024PF30156-Abroad

[0158] - 22 - Preferred rubbers are diene rubbers, for example based on butadiene and isoprene, or copolymers of butadiene and / or isoprene with other copolymerizable monomers.

[0159] Mixtures of different rubbers described above are also suitable.

[0160] Particularly preferred as rubber are pure polybutadiene rubber or styrene-butadiene block copolymer rubber.

[0161] Particularly preferred rubber-modified vinyl(co)polymers are ABS polymers containing structural building blocks derived from acrylonitrile (A), butadiene (B), and styrene (S), wherein these ABS polymers consist of AB S graft polymers and optionally styrene-acrylonitrile copolymers and may further optionally contain MBS graft polymers (methyl methacrylate-butadiene-styrene) with a Kem shell structure, as described, for example, in DE-OS 2 035 390 (=US-PS 3 644 574) or in DE-OS 2248 242 (=GB-PS 1 409275) or in Ullmanns, Enzyklopädie der Technischen Chemie, Vol. 19 (1980), p. 280 ff. Particularly preferred are ABS polymers which contain at least 50 wt.%, more preferably at least 80 wt.%, and especially preferably at least 90 wt.%, in each case based on the ABS polymer, rubber-modified vinyl(co)polymers produced by bulk polymerization.

[0162] Other suitable rubber-modified vinyl(co)polymers are or contain ABS polymers produced by redox initiation with an initiator system of organic hydroperoxide and ascorbic acid according to US-P 4937285.

[0163] The rubber-free vinyl(co)polymer in component B preferably has a medium molecular weight M w (Weight average, determined by GPC with polystyrene as standard) between 15,000 and 250,000 g / mol, preferably in the range of 80,000 to 200,000 g / mol

[0164] The proportion of this rubber-free vinyl(co)polymer in component B amounts to up to 90 wt%, based on component B. It can be determined from the gel content of component B (proportion of rubber-free vinyl(co)polymer = 100 wt% - gel content of the product in wt%), whereby the gel content is determined at 25°C in a suitable solvent (such as acetone) as the insoluble fraction.

[0165] In a preferred embodiment, component B has a lithium content of >1 mg / kg, more preferably > 2 mg / kg. In a further preferred embodiment 2024PF30156-Abroad

[0166] - 23 -the total content of other alkali metals in component B is < 20 mg / kg, particularly preferably < 10 mg / kg.

[0167] The alkali metal content is determined by inductively coupled plasma optical emission spectrometry (ICP-OES) with an internal standard. For this purpose, the sample is digested in concentrated nitric acid in a microwave at 200°C and 200 bar, diluted to 1 M nitric acid, and measured.

[0168] Component C

[0169] Component C is a sulfonic acid or an anhydride of a sulfonic acid. The sulfonic acid can also be used in the form of a hydrate.

[0170] The sulfonic acid preferably used is an organic sulfonic acid of the general structure (9)

[0171] O x ,O

[0172] ''Q Z

[0173] R

[0174]

[0175] / X O-R2< 9 >

[0176] where Ri stands for Ci-30 alkyl, Ce-so-aryl, C7-30 alkylaryl or C7-30 arylalkyl and R2 stands for hydrogen.

[0177] The sulfonic acid is preferably an aromatic sulfonic acid and Ri is selected from the group consisting of phenyl, toluyl, cresyl, xylenyl, propylphenyl, butylphenyl and tert-butylphenyl.

[0178] In the case of the equally suitable sulfonic acid anhydrides, R2 stands for SO2-R3, where R3 has the meaning given for the sulfonic acids and Ri and R3 can be the same or different.

[0179] Component C preferably contains benzenesulfonic acid and / or a hydrate of benzenesulfonic acid. Component C also preferably contains p-toluenesulfonic acid and / or a hydrate of p-toluenesulfonic acid.

[0180] In a particularly preferred embodiment, component C consists of benzenesulfonic acid and / or a hydrate of benzenesulfonic acid. In an equally preferred embodiment, component C consists of p-toluenesulfonic acid and / or a hydrate of p-toluenesulfonic acid. 2024PF30156-Abroad

[0181] - 24 - Component D

[0182] The composition can contain as component D one or more additives different from component C and / or different polymeric components from components A and B, preferably selected from the group consisting of flame retardants (e.g., organic phosphorus or halogen compounds, in particular bisphenol A-based oligophosphate), anti-dripping agents (e.g., compounds of the substance classes of fluorinated polyolefins, silicones, and aramid fibers), flame retardant synergists (e.g., nanoscale metal oxides), smoke inhibitors (e.g., zinc borate), lubricants and demolding agents (e.g., pentaerythritol tetrastearate), nucleating agents, antistatic agents or conductivity additives, and other stabilizers (e.g.,Hydrolysis, heat aging and transesterification stabilizers, UV stabilizers, various Brønsted acid compounds of component C, flow promoters, compatibility agents, antibacterial additives (e.g. silver or silver salts), scratch-resistant additives (e.g. silicone oils), IR absorbents, optical brighteners, fluorescent additives, polymeric blending partners, dyes and pigments, as well as fillers and reinforcing agents (e.g. carbon fibers, talc, mica, kaolin, CaCOs).

[0183] In a preferred embodiment, the composition contains at least one polymer additive selected from the group consisting of lubricants and demolding agents, stabilizers, flame retardants, anti-dripping agents, flow promoters, compatibility agents, as well as dyes and pigments.

[0184] In a preferred embodiment, the composition is free of fillers and reinforcing agents. In a further preferred embodiment, the composition is free of polymeric blending partners other than components A and B, with reactive functional groups selected from the group consisting of epoxy groups, anhydride groups, carboxyl groups, and hydroxy groups.

[0185] Further preferably, the composition contains no polymer additives other than lubricants and demolding agents, stabilizers, flow promoters, flame retardants, anti-drip agents, compatibility enhancers, as well as colorants and pigments, and no polymeric blend partners other than components A and B with reactive functional groups selected from the group consisting of epoxy groups, anhydride groups, carboxy groups, and hydroxy groups. 2024PF30156-Abroad

[0186] - 25 - Particularly preferably, the composition contains no polymer additives other than lubricants and demolding agents, stabilizers, as well as dyes and pigments, and no polymeric blend partners different from components A and B with reactive functional groups selected from the group consisting of epoxy groups, anhydride groups, carboxyl groups and hydroxy groups.

[0187] The composition preferably contains no polymer additives other than lubricants and demolding agents, stabilizers, as well as dyes and pigments, and no polymer blend partners other than components A and B.

[0188] Production of molding compounds and molded parts

[0189] Thermoplastic molding compounds can be produced from the compositions according to the invention.

[0190] The thermoplastic molding compounds according to the invention can be produced, for example, by melting and mixing the respective components of the compositions in a known manner a) preferably at a temperature in the range of 200°C to 350°C, particularly preferably at 240°C to 320°C, most preferably at 260°C to 300°C and b) subsequently solidifying the composition by cooling the melt composition.

[0191] This process is preferably carried out in conventional units such as internal kneaders, extruders, and twin-screw extruders. This process is generally referred to as (melt) compounding or (melt) extrusion.

[0192] Molding compound is therefore understood to be the product that is obtained when the components of the composition are melt compounded and melt extruded.

[0193] The mixing of the individual components of the compositions can be carried out in a known manner, both successively and simultaneously, at approximately 20°C (room temperature) as well as at higher temperatures. This means, for example, that some of the components can be metered via the main feed of an extruder, and the remaining components can be added later in the compounding process via a side extruder.

[0194] Another object of the present invention is therefore a method, as described above, for producing a thermoplastic molding compound from a composition as described above, comprising components A, B, C and optionally D. 2024PF30156-Abroad

[0195] - 26 - Preferably, the melting and mixing is carried out in a continuous twin-screw extruder. Equally preferably, the melting and mixing is carried out with a residence time in the range of 10 seconds to 2 minutes, and more preferably from 15 seconds to 1 minute.

[0196] During melting and mixing, the molten mixture can also be degassed by applying a vacuum. The absolute pressure is preferably set to a maximum of 400 mbar, more preferably to a maximum of 200 mbar, and most preferably to a maximum of 100 mbar.

[0197] Another object of the present invention is a thermoplastic molding compound produced from a composition according to the invention or obtainable by the method according to the invention.

[0198] The molding compounds developed according to the invention can be used to produce molded parts of all kinds. These can be manufactured, for example, by injection molding, extrusion, and blow molding processes. Another form of shaping is the production of molded parts by deep drawing from previously manufactured sheets or films. The molding compounds developed according to the invention are particularly suitable for processing in the injection molding process.

[0199] It is also possible to dose the components of the compositions directly into an injection molding machine or an extrusion unit and process them into molded bodies.

[0200] Examples of such molded parts that can be produced from the inventive compositions and molding compounds include films, protrusions, and molded parts of all kinds, e.g., for the transportation sector, especially automotive engineering, the electrical / electronics sector, the construction sector, household appliances, and medical technology. The inventive compositions and molding compounds are particularly suitable for the production of automotive components for both interior and exterior applications.

[0201] The following are specific embodiments of the present invention.

[0202] 1. Composition containing

[0203] A) Aromatic polycarbonate and / or polyester carbonate, each containing structural units derived from bisphenol A,

[0204] B) rubber-modified vinyl(co)polymer and 2024PF30156-foreign

[0205] - 27 - C) a sulfonic acid and / or a sulfonic anhydride,

[0206] where component C is used in a quantity of 0.0015 to 0.02 parts by weight, based on a total of 100 parts by weight of components A and B.

[0207] 2. Composition according to formulation 1, wherein component A has a proportion of phenolic OH end groups of at least 200 mg / kg.

[0208] 3. Composition according to formulation 1, wherein component A has a proportion of phenolic OH end groups of at least 400 mg / kg.

[0209] 4. Composition according to one of the preceding embodiments, wherein component A contains Fries structures according to at least one of formulas (IV) to (VII).

[0210] (IV)

[0211] (V)

[0212] (VI)

[0213] (VII)

[0214]

[0215] 2024PF30156-Abroad

[0216] - 28 -

[0217] in which the phenyl rings can be independently substituted once or twice with CI - C8 alkyl, or halogen and

[0218] where A stands for

[0219] Ci to Cs-alkylene, C2 to Cs-alkylidene, Cs to Ce-cycloalkylidene, Ce to Cn-arylene, to which further aromatic rings, possibly containing heteroatoms, may be fused, a single bond, -O-, -SO-, -CO-, -S-, -SO2-,

[0220] or a remainder of formula (2) or (3)

[0221] (3)

[0222]

[0223] CH3

[0224] where

[0225] R 5 and R 6 for each X 1 individually selectable, independently of each other hydrogen or C to C6 alkyl,

[0226] XL carbon and

[0227] m means an integer from 4 to 7,

[0228] with the proviso that at least one atom X 1 , R 5and R 6 are simultaneously alkyl, wherein component A contains the structural units (IV) to (VII) in a total amount of 50 to 10000 mg / kg, based on the sum of the wt. fractions of the polycarbonates and polyester carbonates contained in component A.

[0229] 5. Composition according to one of the preceding embodiments, wherein component A is produced by melt polymerization. 2024PF30156-Abroad

[0230] - 29 - 6. Composition according to one of the preceding embodiments, wherein component B is an ABS polymer or a mixture of ABS polymer and MBS graft polymer with Kem shell structure.

[0231] 7. Composition according to one of the preceding embodiments, wherein the composition contains lithium in a concentration of > 0.5 mg / kg.

[0232] 8. Composition according to one of the preceding embodiments, wherein component B has a lithium content of > 1 mg / kg.

[0233] 9. Composition according to one of the preceding embodiments, wherein component B has a content of alkali metals other than lithium and alkaline earth metals totaling < 20 mg / kg.

[0234] 10. Composition according to any of the preceding embodiments, wherein component B contains a rubber-modified vinyl(co)polymer produced by bulk polymerization.

[0235] 11. Composition according to any of the preceding embodiments, wherein component B contains at least 50 wt%, based on component B, of rubber-modified vinyl (co)polymer produced by bulk polymerization. 12. Composition according to any of the preceding embodiments, wherein component B contains at least 80 wt%, based on component B, of rubber-modified vinyl (co)polymer produced by bulk polymerization. 13. Composition according to any of the preceding embodiments, wherein component B contains at least 90 wt%, based on component B, of rubber-modified vinyl (co)polymer produced by bulk polymerization. 14. Composition according to any of the preceding embodiments, wherein component B is a rubber-modified vinyl (co)polymer produced by bulk polymerization.

[0236] 15. Composition according to any of the preceding embodiments, wherein component C is an aromatic sulfonic acid, the hydrate of an aromatic sulfonic acid, the anhydride of an aromatic sulfonic acid or a mixture of several such compounds.

[0237] 16. Composition according to any of the preceding embodiments, wherein component C is selected from the group consisting of benzenesulfonic acid, p-toluenesulfonic acid, hydrates of benzenesulfonic acid and p-toluenesulfonic acid, p-toluenesulfonic anhydride and mixtures thereof.

[0238] 17. Composition according to any of the preceding formulations 1 to 14, wherein component C contains benzenesulfonic acid. 2024PF30156-Abroad

[0239] - 30 - 18. Composition according to embodiment 17, wherein component C consists of benzenesulfonic acid and / or a hydrate of benzenesulfonic acid.

[0240] 19. Composition according to one of the preceding embodiments 1 to 14, wherein component C contains p-toluenesulfonic acid.

[0241] 20. Composition according to embodiment 19, wherein component C consists of p-toluenesulfonic acid and / or a hydrate of p-toluenesulfonic acid.

[0242] 21. Composition according to any of the preceding embodiments, wherein component C is used in an amount of 0.0015 to 0.015 parts by weight. 22. Composition according to any of the preceding embodiments, wherein component C is used in an amount of 0.0015 to 0.008 parts by weight. 23. Composition according to any of the preceding embodiments, wherein component C is used in an amount of 0.002 to 0.006 parts by weight.

[0243] 24. Composition according to one of the preceding formulations comprising 30 to 95 parts by weight of component A and 5 to 70 parts by weight of component B, each based on a total of 100 parts by weight of components A and B.

[0244] 25. Composition according to one of the preceding formulations comprising 50 to 75 parts by weight of component A and 25 to 50 parts by weight of component B, each based on a total of 100 parts by weight of components A and B.

[0245] 26. Composition according to one of the preceding embodiments consisting of components A to C and optionally at least one polymer additive different from component C and / or a polymeric component different from components A and B as component D.

[0246] 27. Composition according to embodiment 26 containing 0.01 to 40 parts by weight, based on a total of 100 parts by weight of components A and B, of component D. 28. Composition according to embodiment 26 containing 0.05 to 20 parts by weight, based on a total of 100 parts by weight of components A and B, of component D. 29. Composition according to embodiment 26 containing 0.1 to 10 parts by weight, based on a total of 100 parts by weight of components A and B, of component D.

[0247] 30. Composition according to embodiment 26 comprising 0.2 to 2 parts by weight, based on a total of 100 parts by weight of components A and B, of component D.

[0248] 31. Composition according to one of the preceding embodiments, wherein the composition is free of fillers and reinforcing agents.

[0249] 32. Composition according to one of the preceding embodiments, wherein the composition is free of polymeric blending partners different from components A and B, having reactive functional groups selected from the group consisting of epoxy groups, anhydride groups, carboxyl groups, and hydroxy groups. 2024PF30156-Abroad

[0250] - 31 -

[0251] 33. Composition according to one of the embodiments 27 to 32, wherein the composition as component D includes at least one polymer additive selected from the group consisting of lubricants and demolding agents, stabilizers, flame retardants, anti-dripping agents, flow promoters, compatibility enhancers, as well as dyes and pigments.

[0252] 34. Method for producing a thermoplastic molding compound comprising

[0253] A) an aromatic polycarbonate and / or polyester carbonate, each containing structural units derived from bisphenol A,

[0254] B) rubber-modified vinyl(co)polymer,

[0255] wherein the components are mixed together at a temperature of 200 to 350 °C and melted and dispersed into each other in a compounding unit, characterized in that a sulfonic acid and / or a sulfonic anhydride is added as component C in an amount of 0.0015 to 0.02 parts by weight, based on a total of 100 parts by weight of components A and B,

[0256] wherein the mixing of components A, B, C and optionally of component C different polymer additives and / or of components A and B different polymeric components as component D of the composition takes place in a single step or alternatively the component C is first premixed in a first step with the total amount or a subset of component A at room temperature or at an elevated temperature.

[0257] 35. Molding compound obtained or obtainable from a composition according to one of the forms 1 to 33 or from a process according to form 34.

[0258] 36. Molded bodies obtained from a molding compound according to execution form 35.

[0259] 37. Use of 0.0015 to 0.02 parts by weight of a sulfonic acid and / or a sulfonic anhydride for reducing the free bisphenol A content in a molding compound produced from a composition containing aromatic polycarbonate and / or polyester carbonate, each containing structural units derived from bisphenol A, and rubber-modified vinyl (co)polymer, and / or for reducing the free bisphenol A content in a molded part obtained from such a molding compound, wherein the parts by weight of the sulfonic acid and / or the sulfonic anhydride refer to a total of 100 parts by weight of components A and B. 2024PF30156-Abroad

[0260] - 32 - Examples

[0261] Component Al:

[0262] Linear polycarbonate based on bisphenol A, produced by melt polymerization, with a weight-averaged molecular weight M w of 27,500 g / mol (determined by GPC in methylene chloride against a BPA-PC standard). The Al component contains a total of 750 mg / kg of structural units according to formulas IV to VII. Component Al has a phenolic OH end-group content of 400 mg / kg and is used as granules.

[0263] Component A2:

[0264] Linear polycarbonate based on bisphenol A, produced by interfacial polymerization, with a weight-averaged molecular weight (Mw) of 31,000 g / mol (determined by GPC in methylene chloride against a BPA-PC standard). Component A2 contains no structural units according to any of formulas IV to VII and a phenolic OH end-group content of <100 mg / kg. It is used as a powder.

[0265] Component Bl:

[0266] Acrylonitrile butadiene styrene (ABS) polymer, produced by bulk polymerization, comprising a dispersed phase of polybutadiene-containing rubber particles with inclusions of styrene-acrylonitrile copolymer and a styrene-acrylonitrile copolymer matrix, exhibiting an A:B:S ratio of 22:10:68 wt.% and a gel content, determined as the fraction insoluble in acetone at room temperature, of 20 wt.%. The free, i.e., acetone-soluble, styrene-acrylonitrile copolymer in component Bl has a weight-averaged molecular weight M w(Measured by GPC at room temperature in tetrahydrofuran as solvent with polystyrene as standard) of 165 kg / mol. The mean rubber particle size D50, measured by ultracentrifugation, is 0.85 pm. The melt flow rate (MVR) of component Bl, measured according to ISO 1133 (2012 version) at 220°C with a 10 kg plunger load, is 6 ml / 10 min. Component Bl contains 3 mg / kg Li and a total of less than 10 mg / kg of other alkali metals (each determined by ICP-OES).

[0267] Component CI:

[0268] Benzenesulfonic acid, 98.0% (Sigma-Aldrich Chemie GmbH, Taufkirchen, Germany) 2024PF30156-Abroad

[0269] - 33 - Component C2:

[0270] Glycerol tribenzenesulfonate

[0271]

[0272] The synthesis of component C2 was carried out as described in WO 2019 / 121463 Al.

[0273] Component C3

[0274] p-Toluenesulfonic acid monohydrate, > 98.5% (Sigma-Aldrich Chemie GmbH, Taufkirchen, Germany)

[0275] Component C4

[0276] p-Toluenesulfonic anhydride, 97% (Sigma-Aldrich Chemie GmbH, Taufkirchen, Germany)

[0277] Production and testing of molding compounds from the compositions

[0278] First, powder mixtures of component C and component A2 were prepared in a MIXACO CM 1.5 laboratory container mixer (Dr. Herfeld GmbH & Co. KG, Neuenrade, Germany). The molding compounds were then produced by compounding on a ZSK25 twin-shaft extruder (Coperion GmbH, Stuttgart, Germany). Components Al and B were fed into the extruder's main feed via separate gravimetric granule feeders, and the previously prepared powder mixture was also fed into the extruder's main feeder via a gravimetric powder feeder. With a housing temperature of 260°C, a throughput of 20 kg / h, and a shaft rotation frequency of 400 revolutions per minute, melt temperatures of 285°C were achieved at the extruder's die outlet. During extrusion, the melt was degassed by applying a vacuum of 50 mbar (absolute).

[0279] To determine the free bisphenol A content, the samples were dissolved in dichloromethane and precipitated with methanol. The precipitated polymer fraction was filtered off, and the filtrate was concentrated. The free BPA content in the concentrated filtrate was determined by HPLC with UV detection using an external standard. 2024PF30156-Abroad

[0280] - 34 - BPA was determined both in the granules, which were obtained as a product of melt compounding after cooling and solidification of the extruded melt strand via granulation, and in injection-molded test specimens measuring 60 mm x 40 mm x 2 mm (color sample plates FMP), which were produced on an Arburg injection molding machine (ARBURG GmbH + Co KG, Loßburg, Germany) at a melt temperature of 290°C and with a residence time of 130 seconds using a mold with a film gate on the 40 mm long edge. The mold temperature was 80°C. Before injection molding, the granules used were dried in a forced-air dryer for 4 hours at 110°C.

[0281] The yellowness index (YI) was measured in reflection on these test specimens of dimensions 60 mm x 40 mm x 2 mm according to ISO / CIE 11664-4:2019.

[0282] As a measure of the hydrolysis stability of the compositions, the difference in melt volume flow rates (MVR) was determined, measured before and after a seven-day exposure of the granules from the melt compound to a warm, humid atmosphere at 95°C / 100% relative humidity. The MVR measurements were performed according to ISO 1133-1:2011 at a temperature of 260°C and with a 5 kg ram load. The granules were dried in a vacuum at 90°C for 4 hours before each MVR measurement. The difference is shown as AMVR in the table below. 2024PF30156-Abroad

[0283] - 35 - Table 1: Compositions and their properties

[0284]

[0285] 2024PF30156-Abroad

[0286] - 36 -

[0287] The data in Table 1 show that, with the components Cl, C3, and C4 according to the invention, molding compounds with a low proportion of free bisphenol A were obtained in the claimed quantity range. However, a minimum amount of this component is necessary for this. If the amount is too low (V2), the proportion of free BPA is not sufficiently below the discussed regulatory limit to ensure compliance even when considering measurement fluctuations and even less favorable processing conditions. Conversely, if the proportion of components Cl, C2, or C3 is too high, this has a negative effect on the hydrolysis behavior and the yellowness value (YI) (V6, V7, V12, V13, V16, and V17), without significantly reducing the BPA content further.With the prior art component C2, the BPA level remains higher, even when the amount is increased beyond the range claimed for the inventive component C (V8 and V9). At concentrations effective for the desired BPA reduction, the inventive components Cl, C3, and C4 achieve a better yellow value (YI) compared to the prior art component C2.

Claims

2024PF30156-Abroad - 37 - Patent claims:

1. Composition containing A) Aromatic polycarbonate and / or polyester carbonate, each containing structural units derived from bisphenol A, B) rubber-modified vinyl(co)polymer and C) a sulfonic acid and / or a sulfonic anhydride, where component C is used in a quantity of 0.0015 to 0.02 parts by weight, based on a total of 100 parts by weight of components A and B.

2. Composition according to claim 1, wherein component A has a proportion of phenolic OH end groups of at least 200 mg / kg.

3. Composition according to one of the preceding claims, wherein component A contains Fries structures according to at least one of formulas (IV) to (VII) 2024PF30156-Abroad in which the phenyl rings can be independently substituted once or twice with Ci-Cs-alkyl or halogen and where A stands for Ci to Cs-alkylene, C2 to Cs-alkylidene, Cs to Ce-cycloalkylidene, Ce to Cn-arylene, to which further aromatic rings, possibly containing heteroatoms, may be fused, a single bond, -O-, -SO-, -CO-, -S-, -SO2-, or a remainder of formula (2) or (3)2024PF30156-Abroad - 39 - (2) (3) CH3 where R 5 and R 6 for each X 1 individually selectable, independently of each other hydrogen or C to C6 alkyl, XL carbon and m means an integer from 4 to 7, with the proviso that at least one atom X 1 , R 5 and R 6are simultaneously alkyl, wherein component A contains the structural units (IV) to (VII) in a total amount of 50 to 10000 mg / kg, based on the sum of the wt. fractions of the polycarbonates and polyester carbonates contained in component A.

4. Composition according to one of the preceding claims, wherein component A is produced by melt polymerization.

5. Composition according to any one of the preceding claims, wherein component B is an ABS polymer or a mixture of ABS polymer and MBS graft polymer with a Kem shell structure.

6. Composition according to any one of the preceding claims, wherein the composition contains lithium in a concentration of > 0.5 mg / kg.

7. Composition according to any one of the preceding claims, wherein component B contains at least 50 wt.%, based on component B, of rubber-modified vinyl (co)polymer produced by bulk polymerization. 2024PF30156-Abroad - 40 - 8. Composition according to one of the preceding claims, wherein component C is an aromatic sulfonic acid, a hydrate of an aromatic sulfonic acid, an anhydride of an aromatic sulfonic acid or a mixture of several such compounds.

9. Composition according to any one of the preceding claims, wherein component C consists of benzenesulfonic acid and / or a hydrate of benzenesulfonic acid.

10. Composition according to any one of the preceding claims, wherein component C consists of p-toluenesulfonic acid and / or a hydrate of p-toluenesulfonic acid.

11. Composition according to one of the preceding claims, wherein component C is used in an amount of C 0.0015 to 0.008 parts by weight, based on a total of 100 parts by weight of components A and B.

12. Composition according to any of the preceding claims comprising 30 to 95 parts by weight of component A and 5 to 70 parts by weight of component B, each based on a total of 100 parts by weight of components A and B.

13. Method for producing a thermoplastic molding compound containing A) an aromatic polycarbonate and / or polyester carbonate, each containing structural units derived from bisphenol A, B) rubber-modified vinyl(co)polymer, wherein the components are mixed together at a temperature of 200 to 350 °C and melted and dispersed into each other in a compounding unit, characterized in that a sulfonic acid and / or a sulfonic anhydride is added as component C in an amount of 0.0015 to 0.02 parts by weight, based on a total of 100 parts by weight of components A and B, wherein the mixing of components A, B, C and optionally of component C various polymer additives and / or of components A and B various polymeric components as component D of the composition takes place in a single step, or alternatively, component C is first premixed in a first step with the total amount or a portion of component A at room temperature or at an elevated temperature. 2024PF30156-Abroad - 41 - 14. Molding compound or molded body obtained or obtainable from a composition according to any one of claims 1 to 12 or in a process according to claim 13.

15. Use of 0.0015 to 0.02 parts by weight of a sulfonic acid and / or a sulfonic anhydride for reducing the content of free bisphenol A in a molding compound produced from a composition containing aromatic polycarbonate and / or polyester carbonate, each containing structural units derived from bisphenol A, and rubber-modified vinyl (co)polymer, and / or for reducing the content of free bisphenol A in a molded part obtained from such a molding compound, wherein the parts by weight of the sulfonic acid and / or the sulfonic anhydride relate to a total of 100 parts by weight of components A and B.

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