Composition containing a polycarbonate, polyester carbonate, and / or polyester as well as an olefin-(METH)acrylic acid copolymer and a phosphonium salt

Abstract

The invention relates to a composition containing A) a polymer selected from the group consisting of polycarbonates, polyesters, and polyester carbonates, B) a copolymer containing structural units derived from an olefin and containing structural units derived from acrylic acid and / or methacrylic acid, C) a phosphonium salt according to formula (9), in which R1 represents C1-C10 alkyl, R2, R3, and R4 each represent, independently of one another, C1-C10 alkyl, benzyl, or C6-C12 aryl, An- represents either an anion of a monovalent or polyvalent carboxylic acid, where n = 1, 2 or 3, or a hydroxide ion, and component C is used in a quantity of 0.001 to 1 parts by weight based on a total of 100 parts by weight of components A and B. The invention further relates to a method for producing a thermoplastic molding compound from the composition, to a thermoplastic molding compound produced from the composition or produced using the method according to the invention, to molded bodies containing said molding compound, and to the use of a phosphonium salt according to formula 9 in compositions containing components A and B in order to reduce the surface gloss of molded bodies produced from the compositions.

Description

[0001] 2024PF30061 - Abroad

[0002] - 1 -

[0003] Composition containing polycarbonate, polyester carbonate and / or polyester as well as olefin (meth)acrylic acid copolymer and phosphonium salt

[0004] The present invention relates to a polycarbonate, polyester carbonate and / or polyester composition comprising an olefin-(meth)acrylic acid copolymer and a phosphonium salt, a process for producing a thermoplastic molding compound from the composition, the molding compound itself produced in such a process, molded bodies comprising this molding compound, and the use of the phosphonium salt to reduce the surface gloss and increase the chemical resistance of compositions comprising polycarbonate, polyester carbonate and / or polyester and an olefin-(meth)acrylic acid copolymer.

[0005] Molding compounds containing polycarbonates, polyester carbonate, and / or polyester have been known for many years. These compounds are used to produce molded parts for a wide variety of applications, for example, in the automotive, construction, and electronics sectors.

[0006] Polymer blends can be produced by mixing polycarbonates, polyester carbonate, and / or polyesters with other polymeric components and additives in the melt (compounding). The properties of such polymer blend molding compounds and the resulting molded parts can be varied over a wide range and adapted to the requirements of the respective application by appropriately selecting their composition and manufacturing conditions.

[0007] An interesting group of potential blending partners is the group of polyolefins. Due to the semi-crystalline nature and low glass transition temperatures of these polymers, improvements in mechanical and rheological properties, as well as resistance to chemical influences, can be achieved. Contact with chemicals such as fats or oils is particularly critical when the molded parts produced from the molding compounds are under stress. Experts therefore refer to this as stress crack resistance. This property is highly relevant, for example, for unpainted components because a protective coating is lacking. Furthermore, the surface appearance is determined by the material itself and not by the coating present on painted components. Often, for example, a matte surface finish is preferred in the automotive sector so that fingerprints or dust particles are less visible.

[0008] In practice, however, the use of polyolefins as blending partners for materials such as polycarbonate is limited. It has been shown that polyolefins can only be used in certain minimum quantities (2024PF30061 - Abroad).

[0009] - 2 - must be done in order to realize the aforementioned advantages. Polyolefins are not miscible with polycarbonate, or not completely miscible, even by extrusion in the melt.

[0010] Due to this often-present partial or incompatibility, separate phases form in polycarbonate blends. Depending on the proportions of the respective polymer components, polycarbonate, for example, forms a matrix phase in which the olefin polymer is present in the form of more or less finely dispersed, microscopically visible polymeric phases. The phase interfaces then represent weak points with regard to mechanical properties, and material delamination can also occur.

[0011] Improved compatibility is achieved with copolymers through the copolymerization of olefins with more readily miscible polar monomers such as acrylic acid and methacrylic acid or their corresponding esters, i.e., acrylates and methacrylates. Such copolymers are already described in the prior art as blending partners for polycarbonates.

[0012] US 2021 / 0163739 discloses a copolymer of ethylene and acrylate(s) with a melt flow index (MFI) of greater than or equal to 50 g / 10 minutes, obtained by radical copolymerization under high pressure in a tubular reactor, and methods for its use. Also disclosed is a thermoplastic composition, intended in particular for extrusion or injection molding, comprising one or more copolymers of ethylene and acrylate(s) in a content ranging from 0.1 to 20 wt.%, and one or more thermoplastic polymers such as polycarbonate.

[0013] EP 0216267 discloses thermoplastic compositions suitable for the production of molded bodies, based on mixtures of an aromatic polycarbonate and a copolymer of ethylene and acrylic or methacrylic acid. It is described that articles produced from these compositions are more resistant to delamination than corresponding compositions based on mixtures of polycarbonate and polyethylene.

[0014] EP 0119531 A2 discloses thermoplastic compositions containing aromatic polycarbonate, an olefinic polymer or copolymer, and a third component, which is a copolymer of an olefin and an acrylate, methacrylate, acrylic acid, or methacrylic acid. The third component improves impact strength and weld line strength.

[0015] EP 0271701 A2 discloses a composition containing at least one high molecular weight aromatic polycarbonate and an impact-modifying agent, 2024PF30061 - Abroad

[0016] - 3 - petrol solvent resistant quantity of an ethylene alkyl acrylate in which the ethylene constitutes about 55 to 75 percent by weight and the alkyl acrylate constitutes about 25 to 45 percent by weight, based on the ethylene alkyl acrylate polymer.

[0017] To improve the mechanical properties, especially impact strength and weld line strength, and to reduce material delamination of polymer blends containing polycarbonate and polyolefins or olefin-containing copolymers, the use of certain catalysts is further proposed.

[0018] US 4,496,693 discloses a composition comprising a) an aromatic carbonate polymer, b) a polyolefin or a polyolefin modified with acrylate, methacrylate, acrylic acid or methacrylic acid in sufficient quantity to modify the aromatic carbonate polymer to be impact-resistant, and c) a catalyst quantity sufficient to make a and b compatible, selected from the group consisting of basic compounds of alkali or alkaline earth metals.

[0019] WO 2020 / 212229 Al discloses a process for producing a thermoplastic molding compound containing an aromatic polycarbonate and another polymer containing functional groups, wherein the polymers are melted and mixed in the presence of a phosphonium salt as a catalyst.

[0020] The documents describing the use of such a catalyst do not disclose anything about its influence on stress crack resistance. Furthermore, the aforementioned prior art does not disclose how a property profile advantageous for unpainted applications can be achieved, namely a matte surface appearance and simultaneously good chemical resistance.

[0021] It was therefore desirable to provide a composition for the production of a thermoplastic molding compound from which molded bodies with improved stress crack resistance and lower surface gloss could be produced.

[0022] Preferably, the molding compound should exhibit good processability in injection molding, i.e., low melt viscosity and good process / hydrolysis stability with regard to the release of low-molecular-weight components and / or molecular weight reduction. Equally preferably, the molded parts produced from the molding compound should exhibit good mechanical properties.

[0023] Surprisingly, it was found that a composition containing 2024PF30061 - Abroad

[0024] A) a polymer selected from the group consisting of polycarbonates, polyesters and polyester carbonates,

[0025] B) a copolymer containing structural units derived from an olefin and containing structural units derived from acrylic acid and / or methacrylic acid,

[0026] C) a phosphonium salt according to formula (9) where

[0027] Ri stands for Ci-Cio alkyl,

[0028] R2, R and R each independently stand for Ci-Cio-alkyl, benzyl or Ce-Cn-aryl,

[0029] A n- either an anion of a mono- or polyvalent carboxylic acid with n = 1, 2 or 3 or a hydroxide ion, where component C, based on a total of 100 parts by weight of components A and B, is used in an amount of 0.001 to 1 part by weight to solve the problem according to the invention.

[0030] The term "a polymer" for component A also includes mixtures of the aforementioned polymers polycarbonate, polyester carbonate, and polyester, and / or mixtures of structurally different polycarbonates, polyester carbonates, or polyesters. "A polymer" is therefore to be understood as "at least one polymer." This applies analogously to the other components B, C, and D contained in the inventive composition and their monomer Z structural units.

[0031] In a preferred embodiment, the composition contains

[0032] 50 to 99.5 parts by weight, more preferably 60 to 95 parts by weight, particularly preferably 70 to 92 parts by weight, each based on a total of 100 parts by weight of components A and B, of the component

[0033] A,

[0034] 0.5 to 50 parts by weight, more preferably 5 to 40 parts by weight, particularly preferably 8 to 30 parts by weight, each based on a total of 100 parts by weight of components A and B, of the component

[0035] B. 2024PF30061 - Abroad

[0036] - 5 -

[0037] The composition more preferably contains 0.001 to 0.1 parts by weight, more preferably 0.002 to 0.07 parts by weight, and particularly preferably 0.005 to 0.05 parts by weight, each based on a total of 100 parts by weight of components A and B, and component C.

[0038] Optionally, the composition contains as component D one or more polymer additives and / or further polymeric components different from A and B, preferably in an amount of 0 to 35 parts by weight, more preferably 0 to 20 parts by weight, most preferably 0 to 5 parts by weight, each based on a total of 100 parts by weight of components A and B.

[0039] The respective sets of quantities of the different components C and D can be combined arbitrarily with each other and with the respective corresponding sets of quantities of components A and B.

[0040] It is preferred to combine the areas mentioned first, further preferably the areas mentioned second, and particularly preferably the areas mentioned third of components A to D.

[0041] The narrowest preferred ranges of the weight parts of components A to C in the composition are each advantageous for achieving better mechanical properties, especially multiaxial low-temperature ductility.

[0042] Compositions consisting of at least 98 wt.%, and more preferably at least 99 wt.%, of components A to D are preferred. Compositions consisting of components A to D are particularly preferred.

[0043] Component A

[0044] Component A is a polymer selected from the group consisting of polycarbonates, polyester carbonates and polyesters, preferably selected from the group consisting of polycarbonates and polyester carbonates, particularly preferably selected from the group consisting of polycarbonates.

[0045] 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 2 232 877, DE-A 2 703 376, DE-A

[0046] 2 714 544, DE-A 3 000 610, DE-A 3 832 396; for the production of polyester carbonates, e.g. DE-A

[0047] 3 007 934). 2024PF30061 - Abroad

[0048] The production of polycarbonates suitable as component A according to the invention is carried out, for example, by reacting 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 dihydroxyaryl compounds and / or aliphatic diols with carbonic acid stems, for example, diphenyl carbonate, is possible.

[0049] 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 structure (1) are preferably used.

[0050] (1)

[0051] A a single bond, Ci to Cs-alkylene, C2 to Cs-alkylidene, Cs to Ce-cycloalkylidene, -O- , -SO- , -CO- , -S- , -SO2- , Ce to Cn-arylene, to which further aromatic rings, optionally containing heteroatoms, may be fused, or a residue of structure (2) or (3) 2024PF30061 - Abroad

[0052] B each Ci to Cn-alkyl, preferably methyl, halogen, preferably chlorine and / or bromine x each independently 0, 1 or 2, p 1 or 0 are, and

[0053] R 5 and R 6 for each X 1 Individually selectable, independently of each other hydrogen or Ci to Ce-

[0054] Alkyl, preferably hydrogen, methyl or ethyl,

[0055] XI carbon and m 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.

[0056] Preferred dihydroxyaryl compounds used 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.

[0057] Other preferred dihydroxyaryl compounds used are 4,4'-dihydroxydiphenyl, bisphenol A, 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, and dihydroxyaryl compounds (I) to (III)

[0058] These and other suitable dihydroxyaryl compounds are listed, 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 2 036 052 A, DE 2 211 956 A and DE 3 832 396 A, in FR 1 561 518 A, and in the monograph "H. Schnell, Chemistry and Physics of Polycarbonates, Interscience 2024PF30061 -Ausland".

[0059] - 8 -

[0060] Publishers, New York 1964" as well as in JP 62039 / 1986 A, JP 62040 / 1986 A and JP 105550 / 1986 A.

[0061] 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.

[0062] 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-hydroxyethoxy)ethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,2-dimethylpropane-1,3-diol, and 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.

[0063] Suitable chain termination compounds 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 monoalkylphenols 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.

[0064] The thermoplastic aromatic polycarbonates have medium molecular weights (average weight M). wMolar density (MDI) of preferably 15,000 to 50,000 g / mol, more preferably 20,000 to 35,000 g / mol, particularly preferably 24,000 to 32,000 g / mol, measured by gel permeation chromatography (GPC) using dichloromethane as the solvent, calibrated with linear polycarbonates (from bisphenol A and phosgene) of known molar mass distribution from PSS Polymer Standards Service GmbH, Germany, calibrated 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. 2024PF30061 - Abroad

[0065] - 9 -

[0066] 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.

[0067] Both homopolycarbonates and copolycarbonates are suitable. For the production of copolycarbonates according to the invention as per 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 employed. These are known (US 3,419,634) and can be produced according to methods known from the literature. 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.

[0068] Copolycarbonates produced using diphenols of general formula (3a) are also preferred:

[0069] (3a)

[0070] R 5 for hydrogen or Ci- to C4-alkyl, Ci- to Cs-alkoxy, preferably for hydrogen;

[0071] Methoxy or methyl, stands,

[0072] R 6 , R7 , 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,

[0073] Y represents a single bond, SO2-, -S-, -CO-, -O-, Ci- to Ce-alkylenes, C2- to Cs-alkylidenes, 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-, isopropylidenes, or a C5- to Ce-cycloalkylidene residue which may be substituted once or several times with Ci- to C4-alkyl, 2024PF30061 -Abroad

[0074] - 10 -

[0075] V represents oxygen, C2- to Ce-alkylenes or C3- to Ce-alkylidenes, preferably oxygen or Cs-alkylenes; p, q and r each independently represent 0 or 1 if q = 0; W represents a single bond if q = 1 and r = 0; W represents oxygen, C2- to Ce-alkylenes or Cs- to Ce-alkylidenes, preferably oxygen or Cs-alkylenes if q = 1 and r = 1; W and V each independently represent C2- to Ce-alkylenes or Cs- to Ce-alkylidenes, preferably Cs-alkylenes.

[0076] Z represents a Ci to Ce alkylene, preferably a Cs alkylene, o represents an average number of repeating units of 10 to 500, preferably 10 to 100, and 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 (3a) are linked to one another via terephthalic acid and / or isophthalic acid to form ester groups.

[0077] Particularly preferred are (poly)siloxanes of formulas (4) and (5) where RI stands for hydrogen, Ci to C4 alkyl, preferably for hydrogen or methyl, and particularly preferably for hydrogen,

[0078] R2 independently for aryl or alkyl, preferably for methyl, 2024PF30061 -abroad

[0079] - 11 -

[0080] 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,

[0081] 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 preferably isopropylidenes, n an average number of 10 to 400, preferably 10 and 100, particularly preferably 15 to

[0082] 50 means and m stands for an average number of 1 to 10, preferably 1 to 6 and particularly preferably 1.5 to 5.

[0083] The siloxane block can also preferably be derived from the following structure. where a in formulas (6), (7), (7a) and (8) represents an average number of 10 to 400, preferably 10 to 100, and most preferably 15 to 50. 2024PF30061 -Abroad

[0084] - 12 -

[0085] It is also preferred that at least two identical or different siloxane blocks of the general formulas (6), (7), (7a) or (8) are linked together via terephthalic acid and / or isophthalic acid to form ester groups.

[0086] Likewise, it is preferred if in formula (3a) 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.

[0087] Copolycarbonates with monomer units of formula (3a) and in particular their preparation are described in WO 2015 / 052106 A2.

[0088] Copolycarbonates with monomer units of formula (6) and in particular their preparation are described in WO 2015 / 052106 A2.

[0089] Aromatic dicarboxylic acid dihalides for the production of aromatic 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.

[0090] In addition to the monophenols already mentioned, other suitable chain terminators for the production of aromatic 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.

[0091] The amount of chain terminators is 0.1 to 10 mol% in each case, based on moles of diphenol in the case of phenolic chain terminators and on moles of dicarboxylic acid dichloride in the case of monocarboxylic acid chloride chain terminators.

[0092] In the production of aromatic polyester carbonates, one or more aromatic hydroxycarboxylic acids can be additionally used. 2024PF30061 - Abroad

[0093] - 13 -

[0094] The aromatic polyester carbonates can be either linear or branched in a known manner (see DE-A 2 940 024 and DE-A 3 007 934), but linear polyester carbonates are preferred.

[0095] 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, 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-hydroxyphenyl)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 diphenols used.Phenolic branching agents can be introduced with the diphenols. Acid chloride branching agents can be introduced together with the acid dichlorides.

[0096] In thermoplastic aromatic polyester carbonates, the proportion of carbonate structural units can vary as desired. Preferably, the proportion of carbonate groups is up to 99.9 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 aromatic polyester carbonates can be present in the form of blocks or statistically distributed within the polycondensate.

[0097] Suitable polyesters are preferably aromatic, and more preferably polyalkylene terephthalates. Particularly preferred are reaction products of aromatic dicarboxylic acids or their reactive derivatives, such as dimethyl esters or anhydrides, and aliphatic, cycloaliphatic, or araliphatic diols, as well as mixtures of these reaction products.

[0098] Particularly preferred aromatic polyalkylene terephthalates contain at least 80 wt%, preferably at least 90 wt%, of the dicarboxylic acid component terephthalic acid residues and at least 80 wt%, preferably at least 90 wt%, of the diol component ethylene glycol and / or butanediol-1,4 residues. 2024PF30061 - Abroad

[0099] - 14 -

[0100] The preferred aromatic polyalkylene terephthalates may contain, in addition to terephthalic acid residues up to 20 mol%, preferably up to 10 mol%, residues of other aromatic or cycloaliphatic dicarboxylic acids with 8 to 14 C atoms or aliphatic dicarboxylic acids with 4 to 12 C atoms, such as residues of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, mezzotinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanedioacetic acid.

[0101] The preferred aromatic polyalkylene terephthalates may contain, in addition to ethylene glycol or butanediol-1,4 residues up to 20 mol%, preferably up to 10 mol%, other aliphatic diols with 3 to 12 carbon atoms or cycloaliphatic diols with 6 to 21 carbon atoms, e.g., residues of propanediol-1,3, 2-ethylpropanediol-1,3, neopentyl glycol, pentanediol-1,5, hexanediol-1,6, cyclohexane-dimethanol-1,4, 3-ethylpentanediol-2,4, 2-methylpentanediol-2,4, 2,2,4-trimethylpentanediol-1,3, 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-(4-ß-hydroxyethoxy-phenyl)-propane and 2,2-bis-(4-hydroxypropoxyphenyl)-propane (DE-A 2 407 674, 2 407 776, 2,715,932).

[0102] Aromatic polyalkylene terephthalates prepared solely from terephthalic acid and its reactive derivatives (e.g. its dialkyl esters) and ethylene glycol and / or butanediol-1,4 are particularly preferred, as are mixtures of these polyalkylene terephthalates.

[0103] Preferred mixtures of aromatic polyalkylene terephthalates contain 1 to 50 wt.%, preferably 1 to 30 wt.%, polyethylene terephthalate and 50 to 99 wt.%, preferably 70 to 99 wt.%, polybutylene terephthalate.

[0104] Aromatic polyalkylene terephthalates can be produced using known methods (see, for example, Kunststoff-Handbuch, Volume VIII, p. 695 ff, Carl-Hanser-Verlag, Munich 1973).

[0105] Component A is preferably a polycarbonate, more preferably an aromatic polycarbonate, more preferably an aromatic polycarbonate containing structural units derived from bisphenol-A, and most preferably an aromatic polycarbonate based exclusively on bisphenol-A as the diol component.

[0106] Component B

[0107] Component B of the compositions according to the invention includes a copolymer containing structural units derived from an olefin, preferably an α-olefin, as well as 2024PF30061 - Foreign country

[0108] - 15 -

[0109] Structural units derived from acrylic acid and / or methacrylic acid. This copolymer is also known as olefin-(meth)acrylic acid copolymer.

[0110] Containing structural units “derived from an olefin” means, in the context of this invention, that an olefin is used in the production of component B. The olefin is then covalently incorporated into the polymer chain of the copolymer. For all other monomeric compounds involved in the structure of components A and B, the meaning of “derived from” within the scope of the present invention is to be understood analogously.

[0111] Preferred olefins as components of the copolymers are α-olefins and particularly preferably have between 2 and 10 carbon atoms and can be unsubstituted or substituted with one or more aliphatic, cycloaliphatic or aromatic groups.

[0112] Particularly preferred olefins are selected from the group comprising ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-octene, and 3-methyl-1-pentene. Especially preferred olefins are ethene and propene, with ethene being particularly preferred. Mixtures of the olefins described are also suitable.

[0113] The production of polyolefins has long been known to those skilled in the art. Polyolefins are produced by chain polymerization of the aforementioned olefins, for example by radical polymerization.

[0114] The polymerization can be carried out, for example, at pressures of 1 to 3000 bar and temperatures between 20°C and 300°C, optionally using a catalyst system. Suitable catalysts include mixtures of titanium and aluminum compounds as well as metallocenes.

[0115] By changing the polymerization conditions and the catalyst system, the number of branches, the crystallinity, and the density of the polyolefins can be varied over a wide range. These measures are also familiar to those skilled in the art. The polyolefins can be semi-crystalline or amorphous, and linear or branched.

[0116] Acrylic acid, methacrylic acid, or mixtures thereof (also called acid-containing monomers) can be incorporated into the polymer in various ways, e.g., by radical copolymerization together with the aforementioned olefins or by grafting the acid-containing monomers onto a polyolefin. Furthermore, it is possible to first copolymerize the olefins with acid derivatives containing monomers, such as esters (acrylates or methacrylates), and later chemically release the acid again by ester hydrolysis or basic saponification followed by neutralization of the resulting carboxylate groups. 2024PF30061 - Abroad

[0117] - 16 -

[0118] Due to the various possible processing methods, the copolymers can exhibit either statistically distributed acid-group-containing monomers or a graft or block copolymer structure. Various manufacturing methods are disclosed, for example, in EP 0216267 Al. The term copolymer encompasses all types of polymers containing structural units derived from olefins and derived from at least one acid-group-containing monomer, regardless of the manufacturing method used.

[0119] The content of acrylic acid and / or methacrylic acid in the copolymer is between 1 and 30 wt. %, preferably between 1.5 and 25 wt. %, and particularly preferably between 2 and 9.5 wt. %, the latter being particularly advantageous for achieving favorable mechanical properties.

[0120] In addition to the aforementioned olefins and acrylic acid and / or methacrylic acid, further monomeric compounds polymerizable with these monomers can be copolymerized during the production of component B. Compounds composed of more than two different monomers are also referred to as copolymers within the scope of the present invention.

[0121] Preferably, no other monomers besides olefins, acrylic acid and / or methacrylic acid are used.

[0122] The copolymers preferably contain structural units derived from olefins and methacrylic acid. Lower gloss levels can be achieved with methacrylic acid than with acrylic acid.

[0123] It is also possible that parts of the carboxylic acid groups of acrylic acid and / or methacrylic acid are partially or completely, preferably partially, neutralized by metal cations, for example, selected from sodium, potassium, lithium, magnesium, zinc, or strontium. Sodium or zinc are preferred. Such compounds containing neutralized acid groups are also called ionomers. The proportion of neutralized carboxylic acid groups can range from 5 to 100% and is preferably 10 to 70%. If the metal cation has a valence of two, such as the zinc cation, one metal cation can neutralize two carboxylic acid groups originating from two polymer chains. This allows for ionic bonding of these chains via the metal cation. Commercially, such copolymers containing carboxylic acid groups partially neutralized with metal cations are available under the trade name Surlyn™ (DuPont).

[0124] The copolymers according to component B exhibit melt flow rates (melt mass flow rates) of preferably 1 to 500 g / 10 min, more preferably 2 to 100 g / 10 min, and particularly preferably 2 to 20 g / 10 min, each measured according to DIN EN ISO 1133-1:2022-10 at 190°C and 2.16 kg. 2024PF30061 - Abroad

[0125] - 17 -

[0126] Component C

[0127] Component C is a phosphonium salt according to formula (9). where

[0128] Ri stands for Ci-Cio alkyl,

[0129] R2, R and Rz each independently stand for Ci-Cio-alkyl, benzyl or Ce-Cn-aryl, A n "either represents the anion of a mono- or polyvalent carboxylic acid with n = 1, 2 or 3 or a hydroxide ion.

[0130] Preferably, Ri in formula (9) represents a C1-C4 alkyl group, more preferably, Ri represents a butyl group.

[0131] In another preferred embodiment, the alkyl groups are unbranched.

[0132] Ri is most often used to represent an n-butyl group.

[0133] Preferably, R2, R3 and Rz each represent C1-C10 alkyl independently of each other, further preferably Ri, R2, R3 and R^ each represent C1-C10 alkyl independently of each other.

[0134] In a further preferred embodiment, at least R2, R3 or R4 represents a butyl group; in particular, R2, R3 and R4 are preferred as butyl groups.

[0135] In another preferred embodiment, the alkyl groups are unbranched.

[0136] R2, R3 and R4 are most preferred to each represent an n-butyl group.

[0137] In the most preferred embodiment, Ri, R2, R3 and R4 all represent n-butyl groups.

[0138] A n" in one embodiment stands for a carboxylate, i.e. the anion of a monocarboxylic acid (n=1), dicarboxylic acid (n=2) or tricarboxylic acid (n=3).

[0139] The carboxylic acid can be aliphatic or aromatic. Preferably, the carboxylic acid is aliphatic.

[0140] The carboxylic acid is further preferred if selected from formic acid, acetic acid, prion acid, butyric acid, valeric acid, caproic acid, mezzotinic acid, oxalic acid, malonic acid, fumaric acid, maleic acid and citric acid.

[0141] Monocarboxylic acids and dicarboxylic acids are preferred, monocarboxylic acids are particularly preferred.

[0142] Even more preferably, the carboxylic acid is an aliphatic, saturated carboxylic acid. 2024PF30061 - Abroad

[0143] - 18 -

[0144] The carboxylic acid selected from malonic acid and acetic acid is particularly preferred, with malonate or acetate as the anions. Acetic acid is the most preferred carboxylic acid, with acetate as the anion.

[0145] Equally preferably, component C is tetrabutylphosphonium hydroxide. This component is commercially available as an aqueous solution under CAS 14518-69-5.

[0146] The most preferred component C is tetrabutylphosphonium acetate. This component is registered as CAS 30345-49-4 and is commercially available.

[0147] It can still be advantageous if, as A n "an acetate anion is used and component C is present as an acetic acid complex.

[0148] This component is commercially available under CAS 34430-94-9 and CAS 17786-43-5.

[0149] In this form, component C is a solid at room temperature and can be easily dosed using the inventive method.

[0150] Component D

[0151] In the process according to the invention, component D can be one or more polymer additives as well as other polymeric components different from A and B, preferably selected from the group consisting of flame retardants, anti-dripping agents, flame retardant synergists, smoke inhibitors, lubricants and demolding agents, nucleating agents, polymeric and non-polymeric antistatic agents, conductivity additives, stabilizers (e.g. hydrolysis, heat aging and UV stabilizers as well as transesterification inhibitors), flow promoters, phase compatibility mediators, impact modifiers (both with and without Kem shell structure), polymeric blending partners, fillers and reinforcing agents as well as dyes and pigments.

[0152] When component D is used, it is preferably used in a proportion of 0.1 to 50 wt.%. This proportion is then the sum of all additives and polymeric components used as component D.

[0153] In a preferred embodiment, at least one polymer additive selected from the group consisting of lubricants and release agents, stabilizers, dyes, and pigments is used. In a preferred embodiment, at least one stabilizer selected from the group consisting of sterically hindered phenols, organic phosphites, and sulfur-based co-stabilizers is used.

[0154] Production of molding compounds and molded parts 2024PF30061 - Abroad

[0155] - 19 -

[0156] Thermoplastic molding compounds can be produced from the compositions according to the invention.

[0157] 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, preferably at a temperature in the range of 200°C to 350°C, particularly preferably at 240°C to 320°C, and most preferably at 260°C to 300°C, and subsequently solidifying the composition by cooling the melt composition. This process is preferably carried out in conventional units such as internal kneading machines, extruders, and twin-screw extrusion machines. This process is generally referred to as (melt) compounding or (melt) extrusion.

[0158] Molding compound is therefore understood to be the product that is obtained when the components of the composition are melt compounded and melt extruded.

[0159] 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, while the remaining components can be added later in the compounding process via a side extruder.

[0160] Another object of the present invention is therefore a method for producing a thermoplastic molding compound from a previously described composition according to the invention, comprising components A, B, C and optionally D, comprising the steps a) melting the composition and mixing the components contained therein at a temperature in the range of 200°C to 350°C and b) solidifying the composition by cooling the composition.

[0161] Preferably, in the inventive method, component C is used in an amount of 0.005 parts by weight to 0.05 parts by weight, based on a total of 100 parts by weight of components A and B.

[0162] Process step a) is preferably carried out in a continuous twin-screw extruder. Equally preferably, process step a) is carried out with a residence time in the range of 10 seconds to 2 minutes, and more preferably 15 seconds to 1 minute. 2024PF30061 -Abroad

[0163] - 20 -

[0164] In step a), the composition 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.

[0165] It is also possible for component C to be deactivated or removed in or after step a). This can have the advantage of preventing an undesired further reaction between components A and B during subsequent processing into molded parts. Deactivation can be achieved, for example, by thermal decomposition of component C or by chemical reaction (quenching). Removal can be achieved, for example, by extraction or by thermal decomposition with the formation of volatile decomposition products and subsequent degassing. Granulation can also be carried out after or directly before step b).

[0166] Granulation can be carried out after or directly before step b).

[0167] 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.

[0168] Another object of the present invention is the use of a phosphonium salt according to formula (9) in compositions containing

[0169] A) a polymer selected from the group consisting of polycarbonates, polyesters and polyester carbonates and

[0170] B) a copolymer containing structural units derived from an olefin and containing

[0171] Structural units derived from acrylic acid and / or methacrylic acid for reducing the surface gloss of molded bodies produced from the compositions, characterized in that the phosphonium salt is used in an amount of 0.001 to 1 wt. parts, based on a total of 100 wt. parts of components A and B.

[0172] For this purpose, the phosphonium salt is preferably used in an amount of 0.005 to 0.05 parts by weight.

[0173] The molding compounds according to the invention can be used to produce molded bodies of all kinds. These can be manufactured, for example, by injection molding, expansion molding, and blow molding. Another processing method is the production of molded bodies by deep drawing. 2024PF30061 - Abroad

[0174] - 21 - from previously produced sheets or films. The molding compounds according to the invention are particularly suitable for processing in extrusion, blow molding and thermoforming processes.

[0175] 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 parts.

[0176] Examples of such molded parts that can be produced from the compositions and molding compounds according to the invention are films, profiles, and molded parts of all kinds, e.g., for the transportation sector, especially the automotive industry, the electrical / electronics sector, the construction sector, household appliances, and medical technology. The compositions and molding compounds according to the invention are particularly suitable for the production of automotive components for both interior and exterior applications.

[0177] Further embodiments of the present invention are described below:

[0178] 1. Composition containing

[0179] A) a polymer selected from the group consisting of polycarbonates, polyesters and polyester carbonates,

[0180] B) a copolymer containing structural units derived from an olefin and containing structural units derived from acrylic acid and / or methacrylic acid,

[0181] C) a phosphonium salt according to formula (9)

[0182] (9) where

[0183] Ri stands for Ci-Cio alkyl,

[0184] R2, R and R each independently stand for Ci-Cio-alkyl, benzyl or Ce-Cn-aryl,

[0185] A n- either an anion of a mono- or polyvalent carboxylic acid with n = 1, 2, or 3, or a hydroxide ion, and where component C is used in an amount of 0.001 to 1 part by weight, based on a total of 100 parts by weight of components A and B. 2024PF30061 -Foreign country

[0186] - 22 -

[0187] 2. Composition according to embodiment 1, characterized in that component A has an average molecular weight M w , measured by gel permeation chromatography at room temperature in methylene chloride with bisphenol A-based polycarbonate as standard, has a density of at least 15000 g / mol.

[0188] 3. Composition according to one of the preceding embodiments, characterized in that component B comprises a proportion of acrylic acid and / or methacrylic acid of

[0189] has a wt.% content of 1 to 30%.

[0190] 4. Composition according to one of the preceding embodiments, characterized in that component B comprises a proportion of acrylic acid and / or methacrylic acid of

[0191] has a content of 2 to 9.5% by weight.

[0192] 5. Composition according to one of the preceding embodiments, characterized in that component B has a melt mass flow rate of 1 to 500 g / 10 min at 190 °C and 2.16 kg, determined according to DIN EN ISO 1133-1:2022-10.

[0193] 6. Composition according to one of the preceding embodiments, characterized in that component B has a melt mass flow rate of 2 to 20 g / 10 min at 190 °C and 2.16 kg, determined according to DIN EN ISO 1133-1:2022-10.

[0194] 7. Composition according to one of the preceding embodiments, characterized in that no monomers other than olefins and acrylic acid and / or methacrylic acid are used in the production of component B.

[0195] 8. Composition according to one of the preceding embodiments, characterized in that component B contains structural units derived from methacrylic acid.

[0196] 9. Composition according to one of the preceding embodiments, characterized in that the carboxylic acid groups of component B are partially or completely neutralized.

[0197] 10. Composition according to embodiment 9, characterized in that the carboxylic acid groups of component B are partially neutralized with zinc cations or sodium cations.

[0198] 11. Composition according to one of the preceding embodiments, characterized in that, in the case of component C, Ri, R2, Rs and R4 each independently represent C1-C10 alkyl.

[0199] 12. Composition according to one of the preceding embodiments, characterized in that Ri and / or R2 of component C represent an n-butyl group.

[0200] 13. Composition according to one of the preceding embodiments, characterized in that the anion in component C is a hydroxide ion.

[0201] 14. Composition according to one of the preceding embodiments 1 to 12, characterized in that in component C the A n"Anion selected from the group consisting of acetate and malonate. 2024PF30061 - Abroad"

[0202] - 23 -

[0203] 15. Composition according to one of the preceding embodiments 1 to 12, characterized in that component C is tetra-n-butylphosphonium acetate.

[0204] 16. Composition according to one of the preceding embodiments 1 to 12 or 14 to 15, characterized in that component C is tetra-n-butylphosphonium acetate in the form of the acetic acid complex.

[0205] 17. Composition according to one of the preceding embodiments, characterized in that component A is an aromatic polycarbonate containing structural units derived from bisphenol A.

[0206] 18. Composition according to one of the preceding embodiments, characterized in that component A is an aromatic polycarbonate based exclusively on structural units derived from bisphenol A.

[0207] 19. Composition according to one of the preceding claims, characterized in that component B, based on a total of 100 parts by weight of components A and B, is used in an amount of 0.5 to 50 parts by weight.

[0208] 20. Composition according to any of the preceding claims, optionally further comprising as component D one or more polymer additives and / or further polymeric blend partners different from components A and B, wherein the composition contains the following proportions of components A to D:

[0209] 50 to 99.5 parts by weight of component A,

[0210] 0.5 to 50 parts by weight of component B,

[0211] 0.001 to 0.1 wt. parts of component C and

[0212] 0 to 35 parts by weight of component D, where all parts by weight are based on a total of 100 parts by weight of components A and B.

[0213] 21. Composition according to one of the preceding claims, characterized in that component B, based on a total of 100 parts by weight of components A and B, is used in an amount of 8 to 30 parts by weight.

[0214] 22. Composition according to any one of the preceding claims, wherein the composition contains the following proportions of components A to D:

[0215] 70 to 92 parts by weight of component A,

[0216] 8 to 30 parts by weight of component B,

[0217] 0.005 to 0.05 wt. parts of component C and

[0218] 0 to 5 parts by weight of component D, where all parts by weight are based on a total of 100 parts by weight of components A and B.

[0219] 23. Composition according to one of the previous embodiments, consisting of 98 wt.% of components A to D. 2024PF30061 - Abroad

[0220] - 24 -

[0221] 24. Composition according to one of the previous formulations, consisting of components A to D.

[0222] 25. Method for producing a thermoplastic molding compound from a composition according to one of the preceding embodiments, comprising the steps a) melting the composition and mixing the components contained therein at a temperature in the range of 200°C to 350°C and b) solidifying the composition by cooling the composition.

[0223] 26. Method according to embodiment 25, characterized in that component C, based on a total of 100 parts by weight of components A and B, is used in a quantity of 0.005 parts by weight to 0.05 parts by weight.

[0224] 27. Method according to embodiment 25 or 26, characterized in that process step a) is carried out in a continuous twin-shaft extruder with a residence time in the range of 15 seconds to 1 minute.

[0225] 28. Thermoplastic molding compound produced from a composition according to one of embodiments 1 to 24 or by a method according to one of embodiments 25 to 27.

[0226] 29. Molded body containing a molding compound according to design 28.

[0227] 30. Use of a phosphonium salt according to formula (9) where

[0228] Ri stands for Ci-Cio alkyl,

[0229] R2, R and R each independently stand for Ci-Cio-alkyl, benzyl or Ce-Cn-aryl,

[0230] A n- either represents an anion of a mono- or polyvalent carboxylic acid with n = 1, 2 or 3, or represents a hydroxide ion, in compositions containing

[0231] A) a polymer selected from the group consisting of polycarbonates, polyesters and polyester carbonates,

[0232] B) a copolymer containing structural units derived from an olefin and containing structural units derived from acrylic acid and / or methacrylic acid 2024PF30061 -Abroad

[0233] - 25 - for reducing the surface gloss of molded bodies produced from the compositions, wherein the phosphonium salt is used in an amount of 0.001 to 1 wt. -parts, based on a total of 100 wt. -parts of components A and B.

[0234] 31. Use according to embodiment 30, wherein the phosphonium salt is used in an amount of 0.005 to 0.05 parts by weight, based on a total of 100 parts by weight of components A and B.

[0235] Examples

[0236] Compositions and components used therein

[0237] Component Al

[0238] Linear polycarbonate based on bisphenol-A with a weight-averaged molecular weight M w of 25,000 g / mol (determined by GPC in methylene chloride as solvent against a bisphenol A polycarbonate standard at room temperature).

[0239] Component A2

[0240] Linear polycarbonate based on bisphenol-A with a weight-averaged molecular weight M w of 31,000 g / mol (determined by GPC in methylene chloride as solvent against a bisphenol A polycarbonate standard at room temperature).

[0241] Component B 1

[0242] Plexiglas™ 8H (Evonik Performance Materials GmbH, Darmstadt): Polymethyl methacrylate

[0243] Component B2

[0244] NUCREL™ 0910HS Acid Copolymer (The Dow Chemical Company, Midland, USA) is an ethylene methacrylic acid copolymer with a methacrylic acid content of 9 wt% and a melt flow index of 10 g / 10 min at 190 °C and 2.16 kg.

[0245] Component B3

[0246] ELVALOY™ AC 1609 Acrylate Copolymer (The Dow Chemical Company, Midland, USA) is an ethylene-methyl acrylate copolymer with a methyl acrylate content of 9% by weight and a melt flow index of 6 g / 10 min at 190 °C and 2.16 kg. 2024PF30061 -International

[0247] - 26 -

[0248] Component B4

[0249] NUCREL™ 0411HS Acid Copolymer (The Dow Chemical Company, Midland, USA) is an ethylene methacrylic acid copolymer with a methacrylic acid content of 4 wt% and a melt flow index of 11 g / 10 min at 190 °C and 2.16 kg.

[0250] Component B5

[0251] NUCREL™ 3990 Acid Copolymer (The Dow Chemical Company, Midland, USA) is an ethylene-acrylic acid copolymer with an acrylic acid content of 9.5 wt% and a melt flow index of 10 g / 10 min at 190°C and 2.16 kg.

[0252] Component B6

[0253] NUCREL™ 599 Acid Copolymer (The Dow Chemical Company, Midland, USA) is an ethylene-methacrylic acid copolymer with a methacrylic acid content of 10 wt% and a melt flow index of 450 g / 10 min at 190°C and 2.16 kg.

[0254] Component B7

[0255] NUCREL™ 925 Acid Copolymer (The Dow Chemical Company, Midland, USA) is an ethylene-methacrylic acid copolymer with a methacrylic acid content of 15 wt% and a melt flow index of 25 g / 10 min at 190°C and 2.16 kg.

[0256] Component CI

[0257] Lithium hydroxide monohydrate 98% (Sigma-Aldrich)

[0258] Component C2

[0259] Tetrabutylphosphonium acetate-acetic acid complex (Sachem Inc., Austin, USA)

[0260] Component C3

[0261] Tetrabutylphosphonium acetate solution (Sachem Inc., Austin, USA) contains 40% by weight of tetrabutylphosphonium acetate dissolved in water.

[0262] Component C4

[0263] Tetrabutylammonium acetate 97% (Sigma-Aldrich)

[0264] Component C5

[0265] Tetrabutylphosphonium p-toluenesulfonate >95% (Sigma-Aldrich) 2024PF30061 -Abroad

[0266] - 27 -

[0267] Component C6

[0268] Tetraphenylphosphonium tetraphenylborate >98% (TCI)

[0269] Production of thermoplastic molding compounds and molded parts

[0270] The PC / PMMA and PC / ethylene-acrylic copolymer molding compounds according to Tables 1 and 2 were produced on a ZSK26 MC 18 twin-shaft extruder from Coperion GmbH (Stuttgart, Germany) at a melt temperature at the die exit of approximately 280°C. A vacuum of 100 mbar (absolute) was applied. The residence time of the melt mixture in the extruder was approximately 30 s.

[0271] The molded parts for the tests were produced at a melt temperature of 260°C (optical test pieces) or 280°C (other test pieces) and at a tool temperature of 80°C on an Arburg 270 E injection molding machine.

[0272] Inspection of the molded parts produced from the molding compounds

[0273] The stress cracking (ESC) resistance in rapeseed oil at room temperature served as a measure of chemical resistance. The time to stress crack-induced failure was determined by the appearance of edge cracks or complete fracture of a test specimen measuring 80 mm x 10 mm x 4 mm, injection-molded at a melt temperature of 280°C, and fully immersed in rapeseed oil. This specimen was subjected to an external edge fiber strain (Rf) of 2.4% using a clamping template. The measurement was performed in accordance with ISO 22088 (2006 version). The maximum test duration was 48 hours. If no edge cracks or fracture of the test specimen were observed within this period, the test was considered passed ("no" in the results tables).

[0274] Surface gloss was measured in reflection at a viewing angle of 20° using a Haze-Gloss gloss meter from BYK-Gardner GmbH (Geretsried, Germany) according to DIN 67530 (1982 version) on test specimens measuring 60 mm x 40 mm x 4 mm, injection-molded at 260 °C. A highly polished injection mold was used. 2024PF30061 - Abroad

[0275] -28 - 2024PF30061 - Abroad

[0276] - 29 -

[0277] The data in Table 1 show that significantly lower gloss levels and high chemical resistance are achieved with the inventive component B2 in combination with the inventive components C2 (inventive example 8) and C3 (inventive example 9) than with the components Bl (comparative example 3) and B3 (comparative example 13) described in the prior art. With the inventive component B2 and the component CI described in the prior art in the amount described therein, lower gloss levels are achieved than without component CI (comparative example 5). However, the achieved gloss levels are insufficient to fulfill the objective. While a sufficiently low gloss level is achieved with a higher concentration of component CI (comparative example 6), such compositions do not fulfill the objective with regard to chemical resistance.The component C2 according to the invention also fails to fulfill the objective at low weight fractions of 0.0005 (comparative example 7). The structurally analogous, but not according to the invention, components C4, C5 and C6 also fail to fulfill the objective.

[0278] 2024PF30061 - Abroad

[0279] -30- 2024P30061 - Abroad

[0280] - 31 -

[0281] The data in Table 2 show that the objective can also be achieved with a structurally analogous component B4 containing a lower proportion of methacrylic acid (Example 14 according to the invention). Example 15 according to the invention shows that the objective is achieved not only by a component containing methacrylic acid, but also by a component B5 containing acrylic acid. Examples 16, 17, and 18 according to the invention show that the objective is achieved in a range of 5 to 20 parts by weight of component B, based on a total of 100 parts by weight of components A and B; however, a content of at least 10 parts by weight of component B proves advantageous with regard to the reduction of the gloss level. Examples 19 and 20 show that the objective is also achieved with higher proportions of structural units derived from methacrylic acid in component B of 10 and 15 parts by weight, respectively.The objective is also fulfilled with component B6, although less effectively with regard to reducing the gloss level than with lower proportions of methacrylic acid-derived structural units in component B. Example 19 shows that even with a high melt flow index of 450 g / 10 min for component B6, the objective is still fulfilled, compared to Example 8, which contains the structurally comparable component B2 with a lower melt flow index of only 10 g / 10 min but a higher and therefore less advantageous gloss level. Examples 21, 22, and 23 of the invention show that component C, in a weight fraction of 0.005–0.05 ppm, based on a total of 100 parts by weight of components A and B, fulfills the objective, whereas the use of component C in a weight fraction of 0.0005 ppm, based on a total of 100 parts by weight of components A and B, does not fulfill the objective (Comparative Example 7).

Claims

2024PF30061 - Abroad Patent claims 1. Composition containing A) a polymer selected from the group consisting of polycarbonates, polyesters and polyester carbonates, B) a copolymer containing structural units derived from an olefin and containing structural units derived from acrylic acid and / or methacrylic acid, C) a phosphonium salt according to formula (9) where Ri stands for Ci-Cio alkyl, R2, R and R each independently stand for Ci-Cio-alkyl, benzyl or Ce-Cn-aryl, A n- either represents an anion of a mono- or polyvalent carboxylic acid with n = 1, 2 or 3 or a hydroxide ion, and where component C is used in an amount of 0.001 to 1 part by weight, based on a total of 100 parts by weight of components A and B.

2. Composition according to claim 1, characterized in that component A has an average molecular weight M w , measured by gel permeation chromatography at room temperature in methylene chloride with bisphenol A-based polycarbonate as standard, has a density of at least 15000 g / mol.

3. Composition according to one of the preceding claims, characterized in that component B comprises a proportion of acrylic acid and / or methacrylic acid of 2 to 9.5 wt.%.

4. Composition according to one of claims 1 to 3, characterized in that component B has a melt mass flow rate of 1 to 500 g / 10 min at 190 °C and 2.16 kg determined according to DIN EN ISO 1133-1:2022-10. 2024PF30061 - Abroad - 33 - 5. Composition according to one of the preceding claims, characterized in that component B contains structural units derived from methacrylic acid.

6. Composition according to one of the preceding claims, characterized in that in component C Ri, R2 and Rz each represent C1-C10 alkyl.

7. Composition according to one of the preceding claims, characterized in that in component C the A n "The anion is selected from the group consisting of acetate and malonate.

8. Composition according to one of the preceding claims, characterized in that component C is tetra-n-butylphosphonium acetate or the acetic acid complex of tetra-n-butylphosphonium acetate.

9. Composition according to one of the preceding claims, characterized in that component A is an aromatic polycarbonate containing structural units derived from bisphenol A.

10. Composition according to one of the preceding claims, characterized in that component B, based on a total of 100 parts by weight of components A and B, is used in an amount of 0.5 to 50 parts by weight.

11. Composition according to any of the preceding claims, optionally further comprising as component D polymer additives and / or further polymeric blend partners different from components A and B, wherein the composition contains the following proportions of components A to D: 50 to 99.5 parts by weight of component A, 0.5 to 50 parts by weight of component B, 0.001 to 0.1 wt. parts of component C and 0 to 35 parts by weight of component D, where all parts by weight are based on a total of 100 parts by weight of components A and B.

12. Method for producing a thermoplastic molding compound from a composition containing, A) a polymer selected from the group consisting of polycarbonates, polyesters and polyester carbonates, 2024PF30061 - Abroad - 34 - B) a copolymer containing structural units derived from an olefin and containing structural units derived from acrylic acid and / or methacrylic acid, C) a phosphonium salt according to formula (9) where Ri stands for Ci-Cio alkyl, R2, R and R each independently stand for Ci-Cio-alkyl, benzyl or Ce-Cn-aryl, A n-either an anion of a mono- or polyvalent carboxylic acid with n = 1, 2 or 3 or a hydroxide ion, where component C, based on a total of 100 parts by weight of components A and B, is used in an amount of 0.001 parts by weight to 1 part by weight, comprising the steps a) melting the composition and mixing the components contained therein at a temperature in the range of 200°C to 350°C and b) solidifying the composition by cooling the composition.

13. Method according to claim 12, characterized in that process step a) is carried out in a continuous twin-shaft extruder with a residence time in the range of 15 seconds to 1 minute.

14. Thermoplastic molding compound produced from a composition according to one of claims 1 to 11 or by a method according to one of the preceding claims 12 to 13, and molded bodies containing the molding compound.

15. Use of a phosphonium salt according to formula (9) 2024PF30061 - Abroad - 35 - where Ri stands for Ci-Cio alkyl, R2, R and R each independently stand for Ci-Cio-alkyl, benzyl or Ce-Cn-aryl, A n- either represents an anion of a mono- or polyvalent carboxylic acid with n = 1, 2 or 3, or represents a hydroxide ion, in compositions containing A) a polymer selected from the group consisting of polycarbonates, polyesters and polyester carbonates, B) a copolymer containing structural units derived from an olefin and containing structural units derived from acrylic acid and / or methacrylic acid for reducing the surface gloss of molded bodies produced from the compositions, wherein the phosphonium salt is used in an amount of 0.001 to 1 part by weight, based on a total of 100 parts by weight of components A and B.

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