Thermoplastic composition comprising a copoly(ESTER)carbonate and at least one specific additive

Abstract

The present invention relates to a thermoplastic composition comprising a copoly(ester)carbonate of a specific formula and at least one specific additive. The present application likewise relates to a thermoplastic moulding compound and to a shaped article.

Description

[0001] 2025PF30041 - Abroad

[0002] - 1 - THERMOPLASTIC COMPOSITION CONTAINING A COPOLY(ESTER)CARBONATE AND AT LEAST ONE SPECIAL ADDITIVE The present invention relates to a thermoplastic composition comprising a copoly(ester) carbonate of a specific formula and at least one specific additive. The present application also relates to a thermoplastic molding compound and a molded body.

[0003] It is known that polyesters, polycarbonates, and polyester carbonates exhibit good properties with regard to mechanical properties, heat resistance, and weathering resistance. Each polymer group, depending on the monomers used, possesses certain key characteristics that distinguish such materials. For example, polycarbonates have particularly good mechanical properties, whereas polyesters often show better chemical resistance. Polyester carbonates exhibit property profiles from both of these groups, depending on the monomers chosen. Depending on the choice of reactants, (co)polycarbonates, (co)polyesters, or copoly(ester)carbonates can be formed.

[0004] Aromatic polycarbonates or polyesters often exhibit a good property profile, but show weaknesses regarding aging and weathering resistance. For example, absorption of UV light leads to yellowing and potentially embrittlement of these thermoplastic materials. Aliphatic polycarbonates and polyester carbonates have better properties in this respect, particularly better aging and / or weathering resistance, as well as better optical properties (e.g., transmission). The disadvantage of aliphatic polycarbonates or polyester carbonates is often their low glass transition temperature. Therefore, it is advantageous to use cycloaliphatic alcohols as (co)monomers, as these can generally raise the glass transition temperature somewhat.

[0005] Copolycarbonates and copolyester carbonates made from isosorbide and long-chain aliphatic diols or acids are known. These are described, for example, by Kamps et al. in Macromolecules, 2019, 52, 3187, as well as in US8273849 and EP2203501. However, these often have the disadvantage of limited transparency. They are usually cloudy or opaque. Non-transparent or highly cloudy materials can only be used to a limited extent, or not at all, for optical applications such as lighting applications or for applications in the pharmaceutical sector, such as in Luer locks, stopcocks, and other IV connectors. Therefore, it is not possible to simply replace classic applications of aromatic polycarbonates with such aliphatic polymers. Furthermore, such polymers exhibit

[0006] - 2 - They have a lower surface hardness. This makes them prone to scratching and unsuitable for use in unpainted outdoor applications.

[0007] EP2840102 describes polymers with low water absorption, good heat resistance, and low-temperature toughness. These polycarbonates or copoly(ester)carbonates contain blocks of specific oligocarbonates from diols or specific blocks from oligoesters. Polyester carbonates with long-chain diols or diacids with more than 12 carbon atoms are not specifically described. Properties such as behavior during hot water storage are not addressed. Example 19 of EP2840102 describes an isosorbide-containing copoly(ester)carbonate containing an ester block of terephthalic acid and cyclohexanedimethanol. However, this polymer has only a small proportion (<50 mol%) of bio-based monomers (isosorbide) and a low glass transition temperature (approx. 100 °C).

[0008] The unpublished PCT / EP2024 / 076755 describes a copoly(ester) carbonate that exhibits high stability against water, especially hot water. Simultaneously, the polymer structure is intrinsically weather-resistant, particularly UV-resistant, and thus suitable for outdoor applications. The copoly(ester) carbonate described therein also exhibits high scratch resistance, high resistance to chemicals such as solvents and / or lipid solutions, and high grease resistance, particularly to rapeseed oil. Furthermore, the described copoly(ester) carbonate displays good thermal stability, comparable to that of conventional aromatic polycarbonates. Therefore, this copoly(ester) carbonate could potentially serve a similar range of applications as conventional polycarbonates.

[0009] In the application of classic polycarbonates, properties tailored to the application area are usually given to them through the targeted addition of additives.

[0010] Based on this prior art, the present invention was therefore based on the objective of overcoming at least one, preferably several, of the disadvantages described above. In particular, the present invention was based on the objective of transforming the copoly(ester)carbonate described in the unpublished PCT / EP2024 / 076755 into compositions suitable for various applications. These compositions should exhibit properties tailored to the respective application area. In particular, the compositions should be usable for similar applications as conventional aromatic polycarbonates, especially bisphenol A-based polycarbonates. 2025PF30041 - Foreign

[0011] - 3 - At least one, preferably all, of the above-mentioned problems have been solved by the present invention. It was surprisingly found that the special copoly(ester) carbonate can be transformed into thermoplastic compositions offering a wide range of applications by the suitable addition of additives. In particular, the targeted use of specific additives or additive combinations can provide a thermoplastic composition that offers a tailored range of applications for specific uses. The thermoplastic compositions according to the invention exhibit, in particular, an excellent property profile.Surprisingly, thermoplastic compositions are provided which exhibit good stability against water, preferably hot water, as well as good resistance to grease, lipid solutions, and organic solvents, along with good processability and good UV and weather resistance. Furthermore, the thermoplastic compositions according to the invention exhibit improved surface hardness compared to polycarbonates based on bisphenol A and also compared to prior art structures. This offers the particular advantage that the thermoplastic compositions according to the invention are suitable for outdoor applications. This is especially true without the need for additional painting, as the scratch resistance is high. At the same time, the thermoplastic compositions according to the invention exhibit good processability.They have such a melt viscosity that they can be readily processed, for example in injection molding, without decomposition (due to the good thermal stability of the copoly(ester) carbonate in combination with, for example, at least one antioxidant). This makes them processable almost like conventional aromatic polycarbonate compositions, and thus at least the classic application areas of conventional aromatic polycarbonate compositions can be served. At the same time, the thermoplastic compositions according to the invention can also contain a high proportion of bio-based monomers, since at least units (A) and (C) of the copoly(ester) carbonate can be obtained from bio-based monomers.

[0012] According to the invention, a thermoplastic composition is therefore provided, comprising 2025PF30041 - Abroad

[0013] - 4 - (I) a copoly(ester) carbonate, containing the units (A), (B), (C), optionally (D) and, if necessary, units different from (A), (B), (C) and (D), with

[0014] (CH2) r

[0015]

[0016] where each r and each s independently represents a number between 0 and 4, and each R 1 independently of each other stands for a structure of the formulas (RIA), (RIB), (R1C) or (R1D).

[0017] (RIB),

[0018] (R1C),

[0019]

[0020] (RID),

[0021] where the with

[0022]

[0023] The marked positions in formulas (RIA) to (R1D) are the positions where the (CFfijr group or (CFEjs group) shown in formula (B) is located, and 2025PF30041 abroad

[0024] - 5 -

[0025] O

[0026] #— (O)t — R 2 — (O) t —

[0027]

[0028] (C),

[0029] where both t are independent of R 2 simultaneously either 0 or simultaneously 1, and each R 2 independently of each other stands for an aliphatic group with 16 to 44 carbon atoms, which may contain one or more double bonds,

[0030] ■O .

[0031]

[0032] (D),

[0033] wherein at least partially direct links exist between the units (A), (B), (C), optionally (D) and, where appropriate, units different from (A), (B), (C) and (D), wherein, if a direct link exists between at least two of the units selected from the group consisting of (A), (B), (C) and, where appropriate, (D), the position of the units (A), (B), (C), (D) marked with is then linked to the units marked with

[0034]

[0035] the marked position of these units is linked, with the exception that if t in formula (C) is 0, there is no direct link between two units (C),

[0036] if t in formula (C) is 0, there is no direct link between unit (C) and unit (D) and

[0037] no direct connection exists between two units (D),

[0038] wherein the copoly(ester)carbonate contains 4 to 25 mol% of unit (B), 2 to 14 mol% of unit (C), 0 to 5 mol% of unit (D) and at least 55 mol% of unit (A), wherein the mol% values ​​refer to the total amount of substance of units (A), (B), (C), where applicable (D) and where applicable units other than (A), (B), (C) and (D) and

[0039] (II) at least one additive selected from the group consisting of

[0040] (Ila) a UV absorber selected from the group consisting of benzotriazole compounds, benzophenone compounds, triazine compounds, benzoate compounds, phenyl salicylate compounds, cyanoacrylate compounds, malonic acid ester compounds and oxalanilide compounds,

[0041] (Hb) a sterically hindered amine light stabilizer,

[0042] (IIc) a bluing agent,

[0043] (Ild) an antioxidant, 2025PF30041 - Abroad

[0044] - 6 - (all) a lubricant and release agent selected from the group consisting of fatty acids with 10 to 30 carbon atoms, their fatty acid esters of mono- or polyhydric alcohols, natural animal waxes, natural vegetable waxes, natural petroleum-based waxes, silicone oils and organopolysiloxanes,

[0045] (llf) an acid-containing additive,

[0046] (llg) an OH and acid group scavenger,

[0047] (llh) of an alkaline compound,

[0048] (lli) a reducing agent

[0049] (llj) an antistatic agent selected from the group consisting of polyether esteramides, glycerol monostearate, ammonium salts of dodecylbenzenesulfonic acid, phosphonium salts of dodecylbenzenesulfonic acid, quaternary ammonium salts of a perfluoroalkylsulfonic acid, maleic anhydride monoglyceride and maleic anhydride diglyceride,

[0050] (llk) a colorant selected from the group of inorganic pigments, which include carbon black, titanium oxide, zinc white, iron oxide red, chromium oxide, iron black, titanium yellow, zinc-iron brown, copper-chromium black, copper-iron black and oxide-based pigments, organic pigments and organic dyes, which include phthalocyanine dyes and pigments; condensed polycycles such as azo, thioindigo, perinone, perylene, quinacridone, dioxazine, isoindolinone and quinophthalone dyes and pigments, anthraquinone, perinone, perylene, methine, quinoline, heterocycle and methyl-based dyes and pigments,

[0051] (13) an inorganic filler,

[0052] (llm) a flame retardant selected from the group consisting of phosphorus compound-based, halogen compound-based, metal sulfonate-based and silicon compound-based flame retardants,

[0053] (lln) a polymeric blend partner selected from the group consisting of poly(lactic acid), poly(cyclohexanedimethanol-cyclohexanedicarboxylate), poly(propylene terephthalate), polycarbonates, polyamide 46, polyamide 12, semiaromatic polyamides, rubber-modified graft polymers, vinyl(co)polymers selected from the group of (co)polymers of

[0054] B.1 50 to 99 wt.%, preferably 65 to 85 wt.%, particularly preferably 70 to 80 wt.% based on the (co)polymer of at least one monomer selected from the group of vinyl aromatics, keme-substituted vinyl aromatics and (meth)acrylic acid (C1-C8) alkyl esters and 2025PF30041 - Abroad

[0055] - 7 - B.2 1 to 50 wt.%, preferably 15 to 35 wt.%, particularly preferably 20 to 30 wt.% based on the (co)polymer of at least one monomer selected from the group consisting of vinyl cyanides, (meth)acrylic acid (Cl-C8) alkyl esters, unsaturated carboxylic acids and derivatives of unsaturated carboxylic acids, polyolefins selected from the group consisting of polyethylene, ethylene copolymers, polypropylene and 4-methylpentene-1 resins, polyacetals, poly(amide-imides), poly(ethersulfones), polyimides, poly(phenylene oxide), poly(phenylene sulfide), poly(phenylsulfone), polyetheretherketone, liquid crystalline polyesters, poly(vinyl chloride) and fluorinated resins.

[0056] Surprisingly, it was found that the inventive thermoplastic composition achieves good property profiles even with predominantly aliphatic building blocks in the polymer structure. These inventive thermoplastic compositions surprisingly provide materials that exhibit good stability against water, particularly hot water, as well as good resistance to grease, lipid solutions, and organic solvents, along with good processability and UV and weather resistance. Furthermore, the inventive compositions exhibit improved surface hardness compared to compositions based on polycarbonates containing bisphenol A and also compared to compositions based on prior art structures. This offers the particular advantage that the inventive compositions are suitable for outdoor applications.This is achieved without the need for additional painting, as the scratch resistance is high. This is particularly surprising because copoly(ester)carbonates with the same monomer units, but different proportions of these monomer units, do not exhibit these properties. Likewise, copoly(ester)carbonates containing one less unit of the defined units (A), (B), and (C) also do not exhibit this property profile.

[0057] The inventive compositions exhibit such a melt viscosity that they can be readily processed without decomposition (due to their good thermal stability and, if necessary, the presence of appropriate additives), for example, in injection molding. They are thus processable almost like compositions of classic aromatic polycarbonates, and therefore at least the classic application areas of classic aromatic polycarbonate compositions can also be served with the inventive thermoplastic composition. At the same time, the copoly(ester) carbonates contained in the inventive compositions can also have a high proportion of bio-based components.

[0058] - 8 - monomers, since at least units (A) and (C) can be obtained from bio-based monomers. Likewise, the thermoplastic compositions according to the invention exhibit sufficient mechanical properties, i.e., for example, ductility is present in an unnotched impact test at room temperature.

[0059] Copoly(ester)carbonate (I)

[0060] The invention relates to compositions containing “copoly(ester)carbonates”. The brackets are preferably to be understood as meaning that the invention includes “copolycarbonates or copolyester carbonates”. A person skilled in the art is able to recognize when the polymer used according to the invention has ester groups or not. This depends in particular on whether both “t”s in unit (C) are 1 (then a polycarbonate is formed) or 0 (then a copolyester carbonate is formed).

[0061] The copoly(ester)carbonate (I) used according to the invention comprises the unit (A), with

[0062]

[0063] (A),

[0064] where the positions marked with # and * are the positions at which unit (A) is incorporated into the copoly(ester) carbonate. Preferably, formula (A) is represented by formula (A*) with

[0065]

[0066] where n represents the average number of repeating units and the positions marked with # and * have the meanings described in (A). n greater than 1 is particularly preferred. n greater than 1 to 200 is very preferred, and n greater than 1 to 100 is particularly preferred. This means that the unit (A) can also be a block of several directly linked units (A). The copoly(ester) carbonate used according to the invention particularly preferably has direct links between at least two units (A). 2025PF30041 - Foreign

[0067] - 9 - In the context of the present invention, the term “mean number of repeating units” is known to those skilled in the art. Those skilled in the art know how to determine this parameter. In particular, this parameter can be determined using Maldi-TOF, GPC and / or FI-NMR and / or 13 can be determined using C-NMR. In particular, in 'H-NMR and / or 13¹³C NMR can reveal the average number of repeating units by examining the end groups of potential blocks (i.e., preferably when a block with direct links of the same units is present, and this block has end groups at the beginning and end that have direct links to units different from those under consideration). It is also evident that the number of repeating units (i.e., preferably of a block of identical units) in a polymer molecule can vary. This number also differs from polymer chain to polymer chain. This results in an "average" number of repeating units. Furthermore, experts are aware that the average number of repeating units can be influenced by the molar ratios of the individual structures to one another.Thus, a structure present in the copoly(ester) carbonate according to the invention at a high molar percentage is more likely to be bound to another structure of the same type than a structure present at only a low molar percentage. It is understood that the upper limit of the average number of repeating units can be so high that all structures of the same type are condensed into a single block.

[0068] Preferably, (A) or (A*) is selected from at least one of the structures (Al), (A2) and (A3), wherein

[0069] (A2),

[0070]

[0071] where the positions marked with # and those marked with * have the meanings described in (A) and corresponding brackets are provided for formula (A*). (A) or (A*) is most preferably represented by formula (Al) (possibly with corresponding brackets for formula (A*)). It is clear to the expert that this 2025PF30041 Abroad

[0072] - 10 - Units are derived from / formed from 1,4:3,6-dianhydrohexitols. 1,4:3,6-dianhydrohexitols are generally selected from the group consisting of isomannide, isoidide, and isosorbide. This can be a bio-based structural element, thus offering all the advantages of a bio-based monomer and the resulting polymer (e.g., improved sustainability, as it is accessible from renewable resources). Unit (A) or (A*) is particularly preferably composed of unit (Al). Unit (A) or (A*) is most preferably bio-based.

[0073] Furthermore, the copoly(ester) carbonate used according to the invention comprises the unit O

[0074] # — O - (CH2), — R 1 — (CH2)S - O

[0075] (B)

[0076]

[0077] (B),

[0078] where each r and each s independently represents a number between 0 and 4, preferably between 0 and 3, particularly preferably between 0 and 2, most particularly preferably 0 or 1, and each R 1 independently of each other stands for a structure of the formulas (RIA), (R1B), (R1C) or (R1D).

[0079]

[0080] (RIA),

[0081] where a is 0 or 1, preferably 0,

[0082]

[0083] where b is 0 or 1, preferably 0,

[0084]

[0085] (RIO,2025PF30041 - Abroad)

[0086] - 11 -

[0087] (RID),

[0088] w

[0089]

[0090] where the positions marked with in formulas (RIA) to (R1D) are the positions at which the (CH2) shown in formula (B) is located r -group or (CH2) S -group and where the positions marked with # and those marked with * are the positions at which the unit (B) is incorporated into the copoly(ester)carbonate.

[0091] It is evident that unit (B) can contain more than one of the units (RIA), (RIB), (R1C) or (R1D).

[0092] It is preferred that unit (B) be represented by formula (B*) with

[0093]

[0094] where m represents the average number of repeating units and the positions marked with # and * have the meanings explained in (B). This is particularly preferred if unit (A) also represents unit (A*). Particularly preferred is m greater than 1. Very preferred is m greater than 1 to 80, particularly preferred is m greater than 1 to 50, and most preferred is m greater than 1 to 10.

[0095] Preferably, in unit (B) or (B*), each r and each s independently represents a number between 0 and 2, most preferably 0 or 1, and each R 1 independently of each other for a structure of the formulas (RIA). In particular, it is preferred that r and s in formulas (B) and (B*) respectively are 1 and R 1 In formulas (B) and (B*), the structure of formula (RIA) is represented. Unit (B) or (B*) is particularly preferably represented by the unit (Bl).

[0096]

[0097] where the positions marked with # and those marked with * have the meanings explained in (B). Most preferably, unit (B) consists of unit (Bl). It is apparent to those skilled in the art that this unit (Bl) is one of TCD-dimethanol (also known as TCD alcohol, tricyclodecanedimethanol or [8-(hydroxymethyl)-3-2025PF30041 - foreign country

[0098] - 12 -tricyclo[5.2.1.02,6]decanyl]methanol) represents a derived unit. TCD-dimethanol is generally present as a mixture of isomers. Up to 32 isomers are possible. Depending on the reaction conditions of the polymerization, the initial number and / or types of isomers of the monomer can also change in the resulting polymer. The unit (Bl) is preferably obtained from a mass-balanced TCD-dimethanol. This has the particular advantage that the CCE footprint of the copoly(ester) carbonate used according to the invention can be reduced.

[0099] The copoly(ester)carbonate used according to the invention further comprises the unit (C), wherein

[0100] (O) t R 2 — (O) t

[0101]

[0102] where both t are independent of R 2 simultaneously either 0 or simultaneously 1, and each R 2 independently of one another, each R represents an aliphatic group with 16 to 44 carbon atoms, which optionally contains one or more double bonds, and wherein the positions marked with # and those marked with * are the positions at which the unit (C) is incorporated into the copoly(ester) carbonate. Particularly preferably, each R 2independently of one another for an aliphatic group with 17 to 44 carbon atoms, particularly preferably with 18 to 44 carbon atoms, particularly preferably with 19 to 44 carbon atoms, particularly preferably with 20 to 44 carbon atoms, particularly preferably with 21 to 44 carbon atoms, particularly preferably with 22 to 43 carbon atoms, particularly preferably with 23 to 42 carbon atoms, particularly preferably with 24 to 41 carbon atoms, particularly preferably with 25 to 40 carbon atoms, particularly preferably with 26 to 39 carbon atoms, particularly preferably with 27 to 38 carbon atoms, particularly preferably with 28 to 37 carbon atoms, particularly preferably with 29 to 37 carbon atoms, particularly preferably with 30 to 37 carbon atoms, particularly preferably with 31 to 37 carbon atoms, particularly preferably with 32 to 37 carbon atoms and most preferably with 33 to 37 carbon atoms.

[0103] In the context of the present invention, the term "aliphatic" or "aliphatic group," unless otherwise defined, refers to a hydrocarbon group that does not contain aromatic units. However, this group may contain one or more double bonds. Furthermore, this group may contain one or more... 2025PF30041 - Abroad

[0104] - 13 -exhibit multiple cycles. These cycles may be condensed together (i.e., for example, one or more carbon atoms may belong to two cycles) or linked together by, for example, alkylene or alkylidene groups. This one or more cycles may contain one or more double bonds. However, it should be noted that, by invention, aromatic cycles are not included in the definition of "aliphatic." Furthermore, the one or more cycles, or the aliphatic group itself, may be interrupted by one or more heteroatoms. This, however, is less preferred.

[0105] In the context of the present invention, the term “alkyl” or “alkyl group” preferably refers, unless otherwise specified, to an alkane structure from which one hydrogen atom has been removed. The alkyl group according to the present invention can be linear or branched. It is saturated and therefore comprises only single bonds between the adjacent carbon atoms. The alkyl group preferably includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, neopentyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1,2-Dimethylpropyl, 1-Methylpentyl, 2-Methylpentyl, 3-Methylpentyl, 4-Methylpentyl, 1,1-Dimethylbutyl, 1,2-Dimethylbutyl, 1,3-Dimethylbutyl, 2,2-Dimethylbutyl, 2,3-Dimethylbutyl, 3,3-Dimethylbutyl, 1-Ethylbutyl, 2-Ethylbutyl, 1,1,2-Trimethylpropyl, 1,2,2-Trimethylpropyl, 1-Ethyl- 1-methylpropyl, 1-Ethyl -2-methylpropyl, 1-Ethyl -2-methylpropyl and the like.The selection of these structures may be limited if the number of carbon atoms is defined differently within the scope of the present invention.

[0106] 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. In this context, the two hydrogen atoms removed from the two carbon atoms can be from any carbon atoms in the alkane structure. This means that the two carbon atoms can be adjacent, but need not be. An alkylene group can be linear or branched. It is saturated. If the alkylene group comprises only one carbon atom, it is a methylene group (-CH2-) which is connected to the rest of the molecule via two single bonds.Preferably the alkylene group comprises methylene, ethylene, n-propylene, iso-propylene, n-butylene, sec-butylene, tert-butylene, n-pentylene, 1-methylbutylene, 2-methylbutylene, 3-methylbutylene, neopentylene, 1-ethylpropylene, n-hexylene, 1,1-dimethylpropylene, 1,2-dimethylpropylene, 1,2-dimethylpropylene, 1-methylpentylene, 2-methylpentylene, 3-methylpentylene, 4-methylpentylene, 1,1-dimethylbutylene, 1,2-2025PF30041 - foreign.

[0107] - 14 - Dimethylbutylene, 1,3-dimethylbutylene, 2,2-dimethylbutylene, 2,3-dimethylbutylene, 3,3-dimethylbutylene, 1-ethylbutylene, 2-ethylbutylene, 1,1,2-trimethylpropylene, 1,2,2-trimethylpropylene, 1-ethyl-1-methylpropylene, 1-ethyl-2-methylpropylene, 1-ethyl-2-methylpropylene, and the like. The selection of these structures may be limited if the number of carbon atoms is defined differently within the scope of the present invention. Furthermore, the alkylene group according to the present invention may optionally comprise at least one carbonyl group, optionally at least one halogen atom, and / or optionally be interrupted by at least one heteroatom. Examples of such alkylene groups are -C(=O)-(CH2)4-C(=O)-, -C(=O)-(CH2)3-C(=O)-, -C(=O)-(CH2)2-C(=O)-, -C(CF3)2, -O-(CH2)4-O-, -O-(CH2)3-O-, -O-(CH2)2-O- and the like. However, the aforementioned structures are less preferred according to the invention.Furthermore, the invention also refers to a "cycloalkylene group". The above-mentioned descriptions apply here, with the addition that the group can further comprise one or more cycles. These cycles can be fused together (i.e., for example, one or more carbon atoms can belong to two cycles) or linked together by, for example, alkylene groups. This one or more cycles can have one or more double bonds. In addition, the one or more cycles, or the aliphatic group itself, can be interrupted by one or more heteroatoms. However, this is less preferred.

[0108] 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. The alkylidene group optionally comprises at least one carbon-carbon double bond, optionally at least one carbonyl group, and / or optionally at least one halogen atom. Preferably, the alkylidene group comprises isopropylidene, n-propylidene, isoheptylidene, and the like.

[0109] In the context of the present invention, the term “aralkyl” preferably refers, and unless otherwise specified, in each case independently, to a linear, cyclic, or branched alkyl group which is singly, doubly, or multiply substituted with aryl groups. In the context of the present invention, the term “aryl” preferably refers, and unless otherwise specified, to an aromatic hydrocarbon group. Examples of “aryl” are phenyl, o-, p-, m-toluyl, naphthyl, phenanthryl, or anthracenyl.

[0110] In the context of the present invention, the term “alkoxy” or “alkoxy group” preferably refers, unless otherwise specified, to a linear, cyclic or 2025PF30041 - Abroad

[0111] - 15 -branched alkyl group which is simply bonded to an oxygen atom (-OR). Preferably, alkoxy groups according to the present invention have 1 to 6 carbon atoms. Particularly preferably, alkoxy groups comprise methoxy, ethoxy, α-propoxy, iso-propoxy, n-butoxy, scc-butoxy. / e / - Butoxy, «-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, neo-pentoxy, 1-ethylpropoxy, cyclohexoxy, cyclopentoxy, «-hexoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 1,2-dimethylpropoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-Ethyl- 1-methylpropoxy, 1-Ethyl -2-methylpropoxy or 1-ethyl-2-methylpropoxy. The selection of these structures may be limited if the number of carbon atoms is defined differently within the scope of the present invention.

[0112] Based on the definitions mentioned above, the professional is able to understand further definitions that are not explicitly mentioned above.

[0113] According to the invention, it is preferred that R 2 The formula (C) is represented by the following formula (R2A) with

[0114] CH3

[0115] R 11

[0116] - R 11 — Y— R 11 - I

[0117] R 11

[0118] I

[0119]

[0120] CH3 (R2A),

[0121] where Y represents a bridging structure selected from the group consisting of an alkylene group with 1 to 4 carbon atoms, an alkylidene group with 1 to 4 carbon atoms, and a cycloalkylene group with 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms, wherein the cycloalkylene group optionally contains one or more double bonds and / or is optionally fused to one or more further cycloalkylene groups, wherein the one or more further cycloalkylene groups optionally each have one or more double bonds.

[0122] where the R adjacent to the bridging structure 11 -Groups are bound to any position in the bridging structure and 2025PF30041 - Abroad

[0123] - 16 -where each R 11independently of each other stands for an alkylene group with 1 to 12 carbon atoms or an alkylidene group with 1 to 12 carbon atoms, provided that the structure of formula (R2A) comprises 16 to 44 carbon atoms and wherein the positions marked with , in formula (R2A) are the positions where the (O)t groups shown in formula (C) are located.

[0124] The formula (R2A) is particularly preferred when represented by one of the formulas (R2Aa), (R2Ab), (R2Ac) or (R2Ad), with

[0125]

[0126] where each R 11 and each

[0127]

[0128] the meanings mentioned for (R2A), the cycle of formula (R2Ac) optionally has one or two double bonds, and each cycle of formula (R2Ad) optionally contains one or two double bonds independently of each other. It is also particularly preferred that R 2Formula (C) represents a mixture of at least two different formulas (R2Aa), (R2Ab), (R2Ac) and (R2Ad). This also includes mixtures of different groups that fall under the same formula (for example, two groups that fall under formula (R2Aa)).

[0129] As explained in more detail above, the cycles of the formulas (R2Ac) and / or (R2Ad) can each contain one or two double bonds. This does not usually imply the formation of an aromatic ring. As explained further below, it is possible that if R 2 Formula (C) comprises a mixture of at least two different formulas (R2Aa), (R2Ab), (R2Ac) and (R2Ad), and also contains small amounts of aromatic bridging structures Y according to formula (R2A). However, this is less preferred. 2025PF30041 - Foreign

[0130] - 17 - Each R is particularly preferred 11in formula (R2A) and / or in formulas (R2Aa), (R2Ab), (R2Ac) or (R2Ad) independently for an alkylene group with 1 to 10 carbon atoms, provided that the structure of formula (R2A) and / or in formulas (R2Aa), (R2Ab), (R2Ac) or (R2Ad) comprises 16 to 44 carbon atoms.

[0131] It is also preferred that the R 2 , (R2A), (R2Aa), (R2Ab), (R2Ac) and / or (R2Ad) has unit (C) 21 to 44 carbon atoms. It is equally preferred that the group described by R 2, (R2A), (R2Aa), (R2Ab), (R2Ac) and / or (R2Ad) described group in unit (C) 17 to 44 carbon atoms, particularly preferably 18 to 44 carbon atoms, particularly preferably 19 to 44 carbon atoms, particularly preferably 20 to 44 carbon atoms, particularly preferably 21 to 44 carbon atoms, particularly preferably 22 to 43 carbon atoms, particularly preferably 23 to 42 carbon atoms, particularly preferably 24 to 41 carbon atoms, particularly preferably 25 to 40 carbon atoms, particularly preferably 26 to 39 carbon atoms, particularly preferably 27 to 38 carbon atoms, particularly preferably 28 to 37 carbon atoms, particularly preferably 29 to 37 carbon atoms, particularly preferably 30 to 37 carbon atoms, particularly preferably 31 to 37 carbon atoms, particularly preferably 32 to 37 carbon atoms and especially preferably has 33 to 37 carbon atoms.The expert is able to apply this limited number of carbon atoms to the above-mentioned specifications regarding the number of carbon atoms.

[0132] It is particularly preferred that the different R 11 in the formula (R2A) and / or in the formulas (R2Aa), (R2Ab), (R2Ac) or (R2Ad) comprise a different number of carbon atoms.

[0133] The unit (C) according to the invention is particularly preferably obtained by condensation of dimer fatty acid and / or a dimer diol obtained by reduction of dimer fatty acid.

[0134] The expert knows that dimer fatty acid is a mixture of different acids. The predominant structures look like this. 2025PF30041 - Abroad

[0135] - 18 -

[0136]

[0137] Fully hydrogenated compounds are preferably used. Dimer fatty acids are generally mixtures. They are produced by the condensation of various unsaturated fatty acids. A fatty acid with conjugated double bonds (conjugated acid) is reacted with other unsaturated fatty acids. Conjugated linoleic acids are particularly preferred for this purpose. The reaction usually proceeds via Diels-Alder addition, forming a partially unsaturated C6 ring. Thus, dimer fatty acids initially contain at least one or more double bonds. The mixture of dimer fatty acids can include trimers and monomers of the fatty acids in addition to the dimer. Oleic acid and linoleic acid are particularly preferred for the reaction. The double bonds contained in the dimer fatty acid are generally hydrogenated. 2025PF30041 Foreign

[0138] - 19 - When using dimer fatty acids, the corresponding diphenyl esters are preferably produced, either in a separate step or intermediately.

[0139]

[0140] In this case, it is again preferred to use a mixture of substances containing at least two different diphenyl esters selected from the above diphenyl esters.

[0141] To obtain a dimer diol by reducing dimer fatty acids, the acid groups are reduced to the corresponding alcohol groups. This is a well-known procedure for experts. It should be noted here, with regard to the unit of the formula (C), that this reduces the total number of carbon atoms in group R. 2 The equation differs for dimer fatty acids and for a dimer diol obtained by reduction of dimer fatty acids, even when the same dimer fatty acid is used in both cases. In the case where the dimer fatty acid has 36 carbon atoms, R contains2 34 carbon atoms, because the carbon atoms of the two acid groups are represented once in formula (C) as a (C=O) group and once, for example, in one of the units (A) or (B) as (C=O) groups (at the respective end of the units marked with *). Is the same dimer fatty acid with 362025PF30041 - Abroad

[0142] - 20 - carbon atoms reduced to a dimer diol, so the R 2 According to unit (C), it contains 36 carbon atoms. As a diol, it reacts with a carbonyl source, and the carbon atom of the (C=O) group shown in unit (C) originates from this carbonyl source. It is evident how this can be extended to all units encompassed by unit (C).

[0143] The unit (C) according to the invention is particularly preferably obtained by condensation of dimer fatty acid with 36 carbon atoms and / or a dimer diol with 36 carbon atoms obtained by reduction of dimer fatty acid.

[0144] Dimer fatty acids are commercially available and known, for example, under the trade names Pripol 1009, Pripol 1006, Pripol 1025, Radiacid 0960, Radiacid 0975, Radiacid 0976, Radiacid 0977, Radiacid 0978, and Unidyme 18. The corresponding dimer diols are known, for example, under the trade names Pripol 2030 and 2033. Pripol and Pripol derivatives are produced, as described above, by the oligomerization of unsaturated fatty acids—preferably C18 acids. Dimerization yields a mixture of mono-, di-, and tricarboxylic acids. The monofunctional compounds are usually separated by distillation. Typically, a mixture of 80% difunctional and 20% trifunctional compounds is obtained, which is further purified by distillation to enrich the difunctional compounds. Hydrogenation yields the saturated compounds. Pripol as a dimer fatty acid, or...Dimerdiol is a purified mixture comprising predominantly diacid or diol with 36 carbon atoms.

[0145] Unit (C) can be a bio-based unit, thus offering all the advantages of a bio-based monomer and the resulting polymer (e.g., improved sustainability, as it is derived from renewable resources). Unit (C) is particularly preferred if it is bio-based.

[0146] Furthermore, a unit of formula (D) can be present in the copoly(ester)carbonate used according to the invention, with

[0147]

[0148] where the positions marked with # and * are the positions at which the unit (D) is incorporated into the copoly(ester) carbonate. The unit (D) is present only to a maximum of 5 mol-% in the copoly(ester) carbonate used according to the invention (where mol-%-2025PF30041 - Foreign country

[0149] - 21 - The data refer to the total amount of substance of units (A), (B), (C), optionally (D) and optionally of units different from (A), (B), (C) and (D). Unit (D) is particularly preferably present in an amount of 0 to 5 mol%, more preferably in an amount of 0 to 3 mol%, more preferably in an amount of 0.01 to 2 mol% and most preferably in an amount of 0 mol% in the copoly(ester) carbonate used according to the invention.

[0150] Unit (D) can be formed by the condensation of cyclohexanedicarboxylic acid into the copoly(ester) carbonate used according to the invention. However, it was found that an excessively high molar fraction of unit (D) in the copoly(ester) carbonate used according to the invention leads to a deterioration of its hot water resistance. Therefore, it is preferable to keep the fraction of unit (D) in the copoly(ester) carbonate used according to the invention as low as possible.

[0151] The copoly(ester) carbonate used according to the invention has at least partial direct links between units (A), (B), (C), optionally (D), and optionally units different from (A), (B), (C), and (D). In this way, it is apparent to a person skilled in the art that a polymer is formed which has carbonate groups and optionally also ester groups. According to the present invention, the term "direct link" is preferably understood to mean that the aforementioned units are directly linked to one another. This is preferably achieved by not having any further unit between the specified units. For example, a unit (A) can have a direct link to a unit (B) by the position of unit (A) marked with * being directly connected to the position of unit (B) marked with #, forming a carbonate group.

[0152] The invention stipulates that if there is a direct link between at least two of the units selected from the group consisting of (A), (B), (C) and, if applicable, (D), the position of units (A), (B), (C), (D) marked with “*” is then linked to the position of these units marked with “#”, except that,

[0153] if t in formula (C) is 0, there is no direct connection between two units (C),

[0154] if t in formula (C) is 0, there is no direct link between unit (C) and unit (D) and

[0155] There is no direct link between two units (D). The phrase "at least two units" in this formulation is to be understood as also including direct links between more units, such as direct2025PF30041 - foreign country

[0156] - 22 - Connections (A)-(B)-(C), (A)-(A)-(B)-(C), (A)-(C)-(B)-(B) etc. Through these direct connections, the property profile described above according to the invention is achieved.

[0157] The exception as to why, when t in formula (C) is 0, there is no direct linkage of two units (C) to each other, when t in formula (C) is 0, there is no direct linkage of unit (C) with unit (D), and no direct linkage of two units (D) to each other, is obvious to a person skilled in the art. Unit (C), when t in formula (C) is 0, and unit (D) are obtained by the incorporation of dicarboxylic acids into the copoly(ester) carbonate. This necessarily results in the formation of ester groups. According to the invention, corresponding other linkages of these units are preferably not possible.

[0158] In principle, the positions marked with # or * denote the positions at which the respective unit or structure is incorporated into the copoly(ester) carbonate used according to the invention. It is evident that these positions do not constitute a "group" but merely serve to simplify the representation. To clarify: if, for example, a unit (A) has a direct linkage with a unit (B), then the position of unit (A) marked with * is the oxygen atom next to the position marked with # in unit (B), so that a carbonate group is formed. This can be applied to all other units by those skilled in the art.Since the invention is a copoly(ester) carbonate, the units (A), (B), (C) and optionally (D) form carbonate groups in direct linkage with each other (and optionally ester groups if unit (C) is included in the direct linkage and t is 0 in each case or if unit (D) is present).

[0159] However, the copoly(ester) carbonate used according to the invention provides that only positions marked with # are directly linked to positions marked with *. Furthermore, in the copoly(ester) carbonate used according to the invention, there is no direct link between two units (C) if t in formula (C) is 0. Likewise, there is no direct link between unit (C) and unit (D) if t in formula (C) is 0. Furthermore, there is no direct link between two units (D). If direct links between two units (A) or direct links between two units (B) exist, this can also be expressed using the units (A*) and (B*), respectively, where the integers n and m represent the number of direct links.

[0160] It is particularly preferred that the copoly(ester) carbonate used according to the invention has direct links between units (A) and (C) and that both t in unit (C) are 0. This preferably results in a group in which a 2025PF30041 - Abroad

[0161] - 23 - The dianhydrohexitol group is directly linked via an ester group to, for example, a group derived from dimer fatty acids.

[0162] Preferably the copoly(ester) carbonate used according to the invention comprises structures of unit (ABC)

[0163]

[0164] (ABC),

[0165] where n represents 1, the average number of repetition units, or the preferences described above, R 1, r and s have the meanings detailed for (B*) in all preferences and combinations, and m stands for 1, the average number of repetition units or the preferences described above, and t and R 2for the meanings described for unit (C) in all preferences and combinations. It is apparent to those skilled in the art that this unit (ABC) can be encompassed by the polymer and that further structures may optionally be present in the copoly(ester) carbonate used according to the invention. Furthermore, the sequence of the monomers is preferably not specified. Preferably, according to the invention, the copoly(ester) carbonate has a statistical incorporation of the monomers. In this case, the structure (ABC) can also be present only to a small extent in the copoly(ester) carbonate used according to the invention, because it represents the specific sequence of individual structural elements. Due to certain process variants, differences in reactivity, or the use of certain catalysts, it may happen that the monomers are not incorporated statistically; this is also preferably included in the generic unit (ABC).Preferably, the copoly(ester)carbonate according to the invention comprises structures in which direct linkages of the formulas (A)-(B), (A)-(C), (C)-(B), (A)-(B)-(C), (A)-(Q-(B), (A*)-(B), (A*)-(C), (A*)-(B)-(C), (A*)-(C)-(B), (A*)-(B*), (B*)-(C), (A*)-(B*)-(C), (A*)-(C)-(B*) or any mixtures of two or more of these structures are present.

[0166] It is preferred that the copolycarbonate used according to the invention comprises unit (ABC*), 2025PF30041 - Abroad

[0167]

[0168] where n represents 1, the average number of repetition units, or the preferences described above, R 1 , r and s have the meanings described for (B*) in all preferences and combinations, and m stands for 1, the average number of repetition units, or the preferences described above, R 2for the meanings detailed for unit (C) in all preferences and combinations, and o represents 1, the average number of repetition units, or a number between 1 and 5. It is evident to the expert that the structure shown above (ABC*) can be derived from units (A), (B), and (C), where t in formula (C) is 1.

[0169] It is particularly preferred that the copoly(ester)carbonate used according to the invention comprises unit (AC),

[0170]

[0171] where n stands for 1 or the average number of repetition units and R 2 for the meanings expressed for unit (C) in all preferences and combination possibilities.

[0172] The copoly(ester)carbonate used according to the invention particularly preferably comprises the unit (ABC) and (AC).

[0173] The copoly(ester) carbonate used according to the invention is particularly preferably characterized in that it consists of at least 80 wt.%, particularly preferably at least 85 wt.%, and more preferably at least 90 wt.% of units (A), (B), (C) and optionally (D). Thus, the copoly(ester) carbonate according to the invention 2025PF30041 - Abroad

[0174] - 25 -preferably contains only small amounts of structures other than those of units (A), (B), (C) and optionally (D). It should be noted, however, that the end groups of the copoly(ester) carbonate used according to the invention are preferably excluded. It is possible that the copoly(ester) carbonate used according to the invention may also have functional units other than carbonate groups and optionally ester groups. However, it is further preferred that the copoly(ester) carbonate used according to the invention does not contain any functional units other than carbonate and / or optionally ester groups. Here too, the end groups can be excluded. This means that the maximum of 20 wt%, preferably a maximum of 15 wt%, particularly preferably a maximum of 10 wt%, is not affected.-%, which consist of units different from units (A), (B), (C) and optionally (D), preferably derived from other diols or dicarboxylic acids, which, by incorporation into the copoly(ester) carbonate, in turn lead to carbonate or ester groups.

[0175] According to the invention, the copoly(ester)carbonate contains 4 to 25 mol% of unit (B), 2 to 14 mol% of unit (C), 0 to 5 mol% of unit (D), and at least 55 mol% of unit (A), where the mol% values ​​refer to the total amount of units (A), (B), (C), where applicable (D), and where applicable, units other than (A), (B), (C), and (D). It is apparent to a person competent in the field that these quantities may also refer to all preferences and combinations of preferences for the individual units (A), (B), and (C).

[0176] The copoly(ester) carbonate used according to the invention particularly preferably comprises

[0177] 4 to 25 mol-%, particularly preferably 5 to 20 mol-%, equally preferably 7 to 18 mol-%, most preferably 10 to 15 mol-% or most preferably 8 to 12 mol-% of unit (B),

[0178] 2 to 14 mol%, particularly preferably 3 to 12 mol%, most preferably 3.5 to 7.0 mol% of unit (C) and

[0179] at least 55 mol-%, particularly preferably at least 65 mol-%, equally preferably at least 75 mol-% and most preferably at least 80 mol-% of the unit (A),

[0180] where the mol% values ​​refer to the total amount of substance of units (A), (B), (C), where applicable (D), and where applicable units other than (A), (B), (C), and (D). 2025PF30041 - Foreign country

[0181] - 26 - These stoichiometric ratios ensure that the copoly(ester) carbonate used according to the invention has one or more, preferably all, of the following properties: a high glass transition temperature, good optical properties such as transparency, good mechanical properties such as ductility at room temperature, high thermal stability, good stability in aqueous media, good hot water stability, good grease resistance, good resistance to lipid solutions, and good solvent resistance. This allows the thermoplastic composition according to the invention to have one or more, preferably all, of the properties mentioned above.

[0182] The expert can determine the amounts of the different units in the copoly(ester) carbonate used according to the invention. Preferably, these can be determined by ¹H NMR spectroscopy. Depending on the process for producing the copoly(ester) carbonate, it can be assumed that almost all monomers used react to form the polymer. In particular, the examples have shown that the stoichiometric ratios of the monomers are also found in the resulting polymer. This means that the expert can influence the stoichiometric ratios of the resulting units in the polymer by adjusting the stoichiometric ratios of the monomers used. It is also preferred that the defined mol% in the copoly(ester) carbonate used according to the invention be determined by ¹H NMR spectroscopy. The expert is familiar with this method.The copoly(ester) carbonate can, for example, be dissolved in CDC I3, and the corresponding peaks of the structural units can be identified. Depending on the compounds used, the expert can assign these peaks to the structural units. The ratios and proportions can be determined using the integrals. On the other hand, the required mol% can also be determined from the amounts of substance used and the ratios of the monomers. It must be assumed that all monomers are completely incorporated into the copoly(ester) carbonate in the same ratio. The expert can therefore also adjust the ratio beforehand.

[0183] It is also possible to subsequently determine the stoichiometric ratios of the resulting units in the polymer by means of total saponification. For this purpose, the polymer can, for example, be hydrolyzed under reflux with sodium methoxide. The resulting solution can then be acidified and concentrated to dryness. The residue can be dissolved in suitable organic solvents, and the contained compounds can be analyzed by HPLC. Appropriate calibration and measurement using HPLC are known to those skilled in the art. 2025PF30041 - Abroad

[0184] - 27 - In addition to units (A), (B), (C) and optionally (D), the copoly(ester) carbonate used according to the invention can also comprise further units different from (A), (B), (C) and optionally (D). Preferably, the copoly(ester) carbonate used according to the invention comprises unit (E), wherein

[0185] #— (O)2— x— (O)2

[0186]

[0187] where both z are independently of x simultaneously either 0 or 1, and each x independently represents a linear or branched alkylene group with 4 to 20, preferably 5 to 15, carbon atoms, which may optionally be interrupted by at least one heteroatom; a cycloalkylene group with 4 to 20, preferably 5 to 15, carbon atoms, which may optionally be interrupted by at least one heteroatom, and wherein the cycloalkylene group may optionally contain several cycles; or an aromatic group, and wherein the positions marked with # and those marked with * are the positions at which the unit (E) is incorporated into the copoly(ester) carbonate, except that if z in formula (E) is 0, there is no direct linkage of two units (E) to each other. It is evident to a person skilled in the art that this unit (E) must be different from unit (D).Particularly preferably, x in unit (E) is an aromatic group, more preferably an aromatic group with up to 20 carbon atoms, which may optionally be interrupted by at least one heteroatom. Particularly preferably, x in unit (E) is a structure of the formula (x1), (x2), or (x3).

[0188]

[0189] where the with

[0190]

[0191] The marked positions in formulas (xl), (x2) and (x3) are the positions at which the (O) shown in formula (E) are located. z -Groups are located.2025PF30041 - Abroad

[0192] - 28 - In particular, x in unit (E) is preferably a structure of the formula (xl), (x2) or (x3), where both z are 0 at the same time.

[0193] Likewise, the copoly(ester) carbonate used according to the invention can be branched. This can be influenced by the use of multi-functional alcohols such as glycerol, trimethylolpropane or tris(4-hydroxyphenyl)ethane (THPE) etc. or multi-functional carboxylic acids such as citric acid, trimellitic acid etc. in the synthesis of the copoly(ester) carbonate used according to the invention.

[0194] The copoly(ester) carbonate used according to the invention preferably comprises at most 25 mol%, more preferably at most 20 mol%, further preferably at most 10 mol%, and most preferably at most 5 mol% aromatic groups. However, any end groups present are preferably excluded. It is preferred that unit (E) is present in the copoly(ester) carbonate used according to the invention at most 20 mol%, further preferably at most 10 mol%, and most preferably at most 5 mol%. It is particularly preferred that x in unit (E) is a structure of formula (xl), (x2), or (x3), where both z are simultaneously 0.

[0195] The copoly(ester) carbonate used according to the invention preferably comprises end groups. These are preferably formed by the use of chain terminators during the synthesis. Monofunctional acids or alcohols, including phenols, can be used as chain terminators. The copoly(ester) carbonate used according to the invention particularly preferably comprises end groups of formula (Z).

[0196]

[0197] (Z),

[0198] where each R 7independently of one another, hydrogen, an alkyl group with 1 to 34 carbon atoms, an aralkyl group with 7 to 34 carbon atoms, an aryl group with 6 to 34 carbon atoms, or a -COO-R' group, where R' represents an alkyl group with 1 to 34 carbon atoms, an aralkyl group with 7 to 34 carbon atoms, an aryl group with 6 to 34 carbon atoms, and each q independently represents 1 to 5, and the position marked with # is the position at which the unit (Z) is bonded to the copoly(ester) carbonate. It is evident that the position marked with # is bonded to the position marked with * of the other units. Thus, the copoly(ester) carbonate used according to the invention can form aromatic units as 2025PF30041 - Abroad

[0199] - 29 - End groups. These do not adversely affect the intrinsic weather stability of the polymer, as their concentration is very low. q in unit (Z) 1 is particularly preferred. R is also preferably 7 for hydrogen or for -COOCHs, most preferably for hydrogen. The copoly(ester) carbonate used according to the invention particularly preferably comprises end groups selected from the group consisting of formula (Z), -OH, -COOH, and any mixtures of these groups. It is evident to those skilled in the art that formula (Z) includes, in particular, phenyl ester end groups and / or phenyl carbonate end groups. Free acid or OH end groups can be reduced, for example, by the use of epoxy groups or carbamate derivatives. Such reactions are known to those skilled in the art.

[0200] It is further preferred that the copoly(ester) carbonate used according to the invention is bio-based to at least 50 mol%, particularly preferably to at least 70 mol%, and most preferably to at least 75 mol%. For the purposes of the present invention, the term "bio-based" means that the chemical compound in question is accessible, obtainable, and / or preferably such a renewable and / or regenerative raw material at the filing date. A renewable and / or regenerative raw material is preferably understood to be a raw material that is regenerated by natural processes at a rate comparable to its degradation rate (see CEN / TS 16295:2012). This term serves in particular to distinguish it from raw materials derived from fossil resources, also referred to as petro-based.Whether a raw material is bio-based or petro-based can be determined by measuring carbon isotopes in the raw material, since the relative amounts of the carbon isotope C. 14 lower in fossil raw materials. This can be done, for example, according to ASTM D6866-18 (2018) or ISO 16620-1 to -5 (2015) or DIN SPEC 91236 2011-07. According to the invention, the term "bio-based" is preferably used for compounds which have a C 14 Isotopic content of over 0.1 x 10⁻¹⁰ 12 , especially preferred from over 0.2 x 10' 12 , and especially preferred by those over 0.3 x 10 12 exhibit. In particular, isosorbide and also dimerfetic acid or the dimer diol obtained by reduction of dimerfetic acid are bio-based.

[0201] The copoly(ester) carbonate used according to the invention preferably has a relative solution viscosity above 1.20, particularly preferably from 1.21 to 1.65, more preferably from 1.22 to 1.63, particularly preferably from 1.23 to 1.62, also preferably from 1.26 to 1.55, and most preferably from 1.26 to 1.40. According to the present invention, the relative solution viscosity (prel; also referred to as eta rel) is preferably determined in dichloromethane at a concentration of 5 g / L at 25 °C using an Ubbelohde viscometer. [The2025PF30041 - Ausland]

[0202] - 30 - The determination of relative solution viscosity using an Ubbelohde viscometer is known to skilled personnel. According to the invention, this is preferably carried out in accordance with DIN 51562-3; 1985-05. The flow times of the copoly(ester) carbonate to be measured through the Ubbelohde viscometer are measured in order to subsequently determine the viscosity difference between the polymer solution and its solvent. For this purpose, the Ubbelohde viscometer is first calibrated by measuring the pure solvents dichloromethane, trichloroethylene, and tetrachloroethylene (always at least 3 measurements, at most 9 measurements). The actual calibration is then carried out with the solvent dichloromethane. Subsequently, the polymer sample is weighed out, dissolved in dichloromethane, and the flow time for this solution is then determined three times. The mean value of the flow times is corrected using the Hagenbach correction, and the relative solution viscosity is calculated.

[0203] This preferred relative solution viscosity ensures that the thermoplastic compositions according to the invention, comprising the copoly(ester) carbonate used according to the invention, have sufficient mechanical properties. "Sufficient" in this context means that they exhibit mechanical properties comparable to compositions comprising classic aromatic polycarbonates, in particular ductility in an unnotched impact test at room temperature.

[0204] Additives (II)

[0205] The thermoplastic composition according to the invention comprises at least one additive selected from the group consisting of

[0206] (Ila) a UV absorber selected from the group consisting of benzotriazole compounds, benzophenone compounds, triazine compounds, benzoate compounds, phenyl salicylate compounds, cyanoacrylate compounds, malonic acid ester compounds and oxalanilide compounds,

[0207] (Hb) a sterically hindered amine light stabilizer,

[0208] (llc) a bluing agent,

[0209] (lld) an antioxidant,

[0210] (all) a lubricant and release agent selected from the group consisting of fatty acids with 10 to 30 carbon atoms, their fatty acid esters of mono- or polyhydric alcohols, natural animal waxes, natural vegetable waxes, natural petroleum-based waxes, silicone oils and organopolysiloxanes,

[0211] (llf) an acid-containing additive,

[0212] (llg) an OH and acid group scavenger, 2025PF30041 - Abroad

[0213] - 31 - (llh) of an alkaline compound,

[0214] (lli) a reducing agent,

[0215] (llj) an antistatic agent selected from the group consisting of polyether esteramides, glycerol monostearate, ammonium salts of dodecylbenzenesulfonic acid, phosphonium salts of dodecylbenzenesulfonic acid, quaternary ammonium salts of a perfluoroalkylsulfonic acid, maleic anhydride monoglyceride and maleic anhydride diglyceride,

[0216] (llk) a colorant selected from the group of inorganic pigments, which include carbon black, titanium oxide, zinc white, iron oxide red, chromium oxide, iron black, titanium yellow, zinc-iron brown, copper-chromium black, copper-iron black and oxide-based pigments, organic pigments and organic dyes, which include phthalocyanine dyes and pigments; condensed polycycles such as azo, thioindigo, perinone, perylene, quinacridone, dioxazine, isoindolinone and quinophthalone dyes and pigments, anthraquinone, perinone, perylene, methine, quinoline, heterocycle and methyl-based dyes and pigments,

[0217] (13) an inorganic filler,

[0218] (llm) a flame retardant selected from the group consisting of phosphorus compound-based, halogen compound-based, metal sulfonate-based and silicon compound-based flame retardants,

[0219] (lln) a polymeric blend partner selected from the group consisting of poly(lactic acid), poly(cyclohexanedimethanol-cyclohexanedicarboxylate), poly(propylene terephthalate), polycarbonates, polyamide 46, polyamide 12, semiaromatic polyamides, rubber-modified graft polymers, vinyl(co)polymers selected from the group of (co)polymers of

[0220] B.1 50 to 99 wt.%, preferably 65 to 85 wt.%, particularly preferably 70 to 80 wt.% based on the (co)polymer of at least one monomer selected from the group of vinyl aromatics, keme-substituted vinyl aromatics and (meth)acrylic acid (C1-C8) alkyl esters and

[0221] B.2 1 to 50 wt.%, preferably 15 to 35 wt.%, particularly preferably 20 to 30 wt.% based on the (co)polymer of at least one monomer selected from the group consisting of vinyl cyanides, (meth)acrylic acid (Cl-C8) alkyl esters, unsaturated carboxylic acids and derivatives of unsaturated carboxylic acids, polyolefins selected from the group consisting of polyethylene, ethylene copolymers, polypropylene and 4-methylpentene-1-resins, polyacetals, poly(amide-imides), poly(ethersulfones), polyimides, poly(phenylene oxide), poly(phenylene sulfide), poly(phenylsulfone), 2025PF30041 - Abroad

[0222] - 32 - Polyetheretherketone, liquid crystalline polyesters, poly(vinyl chloride) and fluorinated resins.

[0223] UV absorber (Ila)

[0224] The UV absorber usable according to the invention is selected from the group consisting of benzotriazole compounds, benzophenone compounds, triazine compounds, benzoate compounds, phenyl salicylate compounds, cyanoacrylate compounds, malonic ester compounds, and oxalanilide compounds. These UV absorbers can be used individually or in combination with two or more of them. The molecular weights of these UV absorbers are not particularly limited. The molecular weights are generally 200 g / mol or higher, preferably 250 g / mol or higher, and generally 600 g / mol or lower, preferably 450 g / mol or lower, and even more preferably 400 g / mol or lower. If the molecular weights are too low, the UV resistance of the thermoplastic compositions according to the invention may decrease during long-term use.If the molecular weights are too high, there is a possibility that the transparency of the thermoplastic compositions according to the invention will decrease during long-term use.

[0225] Specific examples of the benzotriazole compounds include 2-(2'-hydroxy-3'-methyl-5'-hexylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-hexylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole, 2-(2'-Hydroxy-3'-methyl-5'-t-octylphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-dodecylphenyl)benzotriazole, 2-(2'-hydroxy-3'-methyl-5'-t-dodecylphenyl)benzotriazole, 2-(2'-hydroxy-5 '-t-butylphenyl)benzotriazole and methyl 3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate.

[0226] Preferred benzotriazole derivatives have the general structure (15)

[0227]

[0228] in the Ri stands for halogen, preferably chlorine, or hydrogen

[0229] R2 and R3 can independently represent hydrogen, alkyl, or aralkyl; n stands for 1 or 2. 2025PF30041 Foreign country

[0230] - 33 - Benzotriazole derivatives suitable according to the invention are offered, for example, by BASF SE (Germany) under the trade names Tinuvin 360, Tinuvin P, Tinuvin 234, Tinuvin 312, Tinuvin 326, Tinuvin 328, Tinuvin 329, Tinuvin 350 and Tinuvin 571.

[0231] Particularly suitable benzotriazole derivatives are the compounds according to structures (16), (17), (18) or (19):

[0232] HO

[0233] (16)

[0234]

[0235] Structure (16) is classified as CAS 2440-22-4 and is commercially available as Tinuvin P (BASF SE, Germany). Structure (17) is classified as CAS 3896-11-5 and is commercially available as Tinuvin 326 (BASF SE, Germany). Structure (18) is classified as CAS 3147-75-92025PF30041 - Abroad

[0236] - 34 -classified and commercially available as Tinuvin 329 (BASF SE, Germany). Structure (19) is available as Tinuvin 360 (BASF SE, Germany) (CAS: 103597-45-1).

[0237] The UV absorber can also be one of the following benzotriazoles:

[0238] 2-[2-hydroxy-3,5-bis(a,a-dimethylbenzyl)phenyl]-2H-benzotriazole (TINUVIN 234), TINUVIN 320 (2-(2H-benzotriazol-2-yl)-4,6-di-tert-butylphenol), 2-[2-hydroxy-3-[( 1 ,3 ,4,5 ,6,7-hexahydro- 1,3 -dioxo-2H-isoindol-2-yl)methyl] -5 -methylphenyl] -2H-benzotriazole (Sumisorb 250), 2-(3,5-di-tert-amyl-2-hydroxyphenyl)benzotriazole (Sumisorb 350), Sumisorb 340, 2,2'-methylenebis[6-(benzotriazol-2-yl)-4-tert-octylphenol] (LA-31), 2-(3'-t-butyl-2'-hydroxy-5'-methylphenyl)-5-chlorobenzotriazole (LA-36, Sumisorb 300), 2-(3',5'-di-t-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole (Tinuvin 327).

[0239] Suitable triazine derivatives according to the invention are offered, for example, by BASF SE (Germany) under the trade names Tinuvin 1577 and Tinuvin 1600, Cyasorb 1164 by Solvay (Brussels, Belgium) and by Adeka Palmarole SAS (Mulhouse, France) under the trade name ADK Stab LA-46.

[0240] Particularly preferred is a 2-(4,6-diaryl-1,3,5-triazin-2-yl)-5-(alkoxy)phenol of the general formula (22)

[0241] ux

[0242] ... j

[0243] - OH

[0244] \ \

[0245] I., ■< | I' — — — iR

[0246]

[0247] (22)

[0248] in the

[0249] R 1 , R 2 and R 3 independently selected for identical or different residues from the group consisting of CI - to C8 alkyl or CI - to C8 aryl,

[0250] n and p independently of each other for an integer from 0 to 5, preferably for 0, 1 or 2, particularly preferably for 0 or 1,

[0251] m for an integer from 0 to 4, preferably for 0 or 1, particularly preferably for 0 and

[0252] R for any organic residue consisting of carbon, hydrogen and optionally oxygen, preferably for CI to C10 alkyl

[0253] stand,

[0254] where R 2 and R 3 preferably for methyl or phenyl, especially preferred for phenyl. A triazine derivative of formula (23)2025PF30041 is particularly preferred - foreign country

[0255] - 35 -

[0256]

[0257] (23).

[0258] This is commercially available under the trade name Tinuvin 1600 (BASF SE, Germany).

[0259] Other preferred triazine compounds include 2-[4-[(2-Hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-l,3,5-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-isooctyloxyphenyl)-s-triazine and 2-(4,6-diphenyl-l,3,5-triazine-2-yl)-5-[(hexyl)oxy]phenol (Tinuvin 1577).

[0260] A preferred UV absorber from the group of hydroxybenzophenone derivatives is the compound 2-hydroxy-4-octoxybenzophenone according to structure (20)

[0261]

[0262] (20)

[0263] It is commercially available as Songsorb 8100 (CAS 1843-05-06, Songwon, Korea). Other commercially available additives of this class are ADK Stab LA-12 (CAS 4221-80-1, Adeka, Japan), ADK Stab LA-51 (CAS 57472-50-1, Adeka, Japan), Lowilite 20 (CAS 131-57-7, Si Group, USA), and Lowilite 24 (CAS 131-56-6, Si Group, USA). 2,2'-Dihydroxybenzophenone and 2,2',4,4'-Tetrahydroxybenzophenone are also preferred. A preferred UV absorber of the cyanoacrylate derivatives is, for example, the compound according to structure (24)2025PF30041 - Foreign

[0264] O

[0265]

[0266] (24).

[0267] It is commercially available as Uvinol 3035 (CAS 5232-99-5, BASF SE, Germany). Another example is 2'-Ethylhexyl-2-cyano-3,3-diphenylacrylate.

[0268] According to the invention, suitable oxalinide-type UV absorbers have the general structure (21)

[0269]

[0270] (21)

[0271] where Ri and R2 can each independently represent alkyl or aralkyl, preferably alkyl with 1 to 10 carbon atoms.

[0272] An example of a commercially available oxalinide-type UV absorber is the compound shown in structure (25) (CAS 23949-66-8, Tinuvin 312, BASF SE, Germany).

[0273]

[0274] The UV absorber is particularly preferred if selected from the group consisting of 2-(2'-Hydroxy-3 '-t-butyl-5 '-hexylphenyl)benzotriazole, 2-(2'-Hydroxy-5'-t-butylphenyl)benzotriazole, 2-[4-[(2-Hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-l,3,5-triazine and 2,2,4,4'-tetrahydroxybenzophenone.

[0275] According to the invention, the at least one UV absorber is preferably used in quantities of 0 to 10 parts by mass, preferably 0.05 to 10.00 parts by mass, more preferably 0.10 to 1.00 parts by mass, even more preferably 0.10 to 0.50 parts by mass and most preferably 0.10 to 0.30 parts by mass, wherein the parts by mass are based on 100 parts by mass of component (I).

[0276] Sterically hindered amine light stabilizers (Ilb)2025PF30041 - Foreign

[0277] The thermoplastic composition according to the invention may contain a sterically hindered amine light stabilizer.

[0278] The sterically hindered amine light stabilizer preferably has a molecular weight of 1,000 g / mol or less. In this case, the weather resistance of the molded part obtained from the thermoplastic composition or molding compound can be further improved. For the same reason, the sterically hindered amine light stabilizer preferably has a molecular weight of 900 g / mol or less. The molecular weight of the sterically hindered amine light stabilizer is preferably 300 g / mol or more. In this case, the heat resistance of the thermoplastic composition according to the invention can be improved. Likewise, contamination of the mold during molding is more reliably prevented. This allows a molded part according to the invention with a better surface finish to be obtained. For the same reason, the molecular weight of the light stabilizer is even more preferably 400 g / mol or more.

[0279] The sterically hindered amine light stabilizer is preferably a compound with a piperidine structure. The piperidine structure defined here need only be a saturated 6-membered amine structure and also includes those in which part of the piperidine structure is replaced by a substituent. Examples of the substituent include an alkyl group with 4 or fewer carbon atoms, with a methyl group being particularly preferred. The sterically hindered amine light stabilizer is even more preferably a compound with several piperidine structures and further preferably a compound in which the several piperidine structures are linked by an ester structure.

[0280] Preferably the sterically hindered amine light stabilizer has one or more structural units according to formula (30),

[0281] Y

[0282]

[0283] (30)

[0284] where in formula (30)

[0285] Y fur H, R 2 or OR 2 stands and

[0286] R 2 stands for branched or unbranched Ci-Cis-alkyl, C2-C2o-alkenyl, Ce-Cn-aryl or -CO-Ci-Ci8-alkyl.

[0287] Examples of such sterically hindered amine light stabilizers are: 4-piperidinol, 2,2,6,6-tetramethyl-4-benzoate, bis(2,2,6,6-tetramethyl-piperidyl)sebacate, bis(1,2,2,6,6-2025PF30041 - Abroad

[0288] - 38 - Pentamethyl-4-piperidyl)sebacat, Tetrakis(2,2,6,6-tetramethylpiperidin-4-carbonsäure)-1,2,3,4-butantetrayl, Kondensationsprodukt aus 2,2,6,6-Tetramethyl-pyrrolidinol, Tridecylalkohol und 1,2,3,4-Butantetracarbonsäure, l,2,2,6,6-Pentamethyl-4-piperidyl und Tridecylalkohol und Tridecyl-1,2,3,4-Butantetracarboxylat, Bis(l,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(l,l-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonat, Decandisäure-bis(2,2,6,6-tetramethyl-l-(octyloxy)-4-piperidinyl)ester, Reaktionsprodukt von 1,1-Dimethylethylhydroperoxid und Octan, l-[2-[3-(3,5-Di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl]-4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl]-2,2,6,6-tetramethylpiperidin, Tetrakis( 1,2, 2,6,6-pentamethyl-4-piperidyl)- 1 ,2,3 ,4-butantetracarboxylat, Poly [ { 6-( 1 , 1 ,3 , 3 -tetramethylbutyl)amino-l,3,5-triazin-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylen{(2,2,6,6-tetramethyl-4-piperidyl)imino}], N, N'-Bis(2, 2,6,6-tetramethyl-4-piperidyl)- 1,6-hexanediamine polymer and 2,4,6-trichloro- 1,3,5-triazine, condensation product of 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl4-piperidinol and β,β,β,β-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5,5]undecane-diethanol), N,N'-bis(3-aminopropyl)ethylenediamine-2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-6-chloro- 1,3,5-triazine condensate and dimethyl- 1 -(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate of succinate.,

[0289] The content of the sterically hindered amine light stabilizer is preferably 0 to 5 parts by mass, particularly preferably 0.001 to 5 parts by mass, where the parts by mass are based on 100 parts by mass of component (I). In this case, the weather resistance of the thermoplastic composition according to the invention, the molding compound produced therefrom, and the molded body produced therefrom can be further improved, and discoloration and the like can be further prevented. This makes it possible, for example, to maintain the deep black color and gloss of the product over a longer weathering period if the thermoplastic composition is colored deep black by the addition of a colorant. Such a thermoplastic composition is suitable, for example, for use in automotive interior and exterior products.The content of the sterically hindered amine light stabilizer is preferably 0.005 to 3 parts by mass, and most preferably 0.01 to 1 part by mass.

[0290] Bluing agent (IIc)

[0291] Thermoplastic compositions can develop a yellow tint due to processing or other thermal damage. To achieve a colorless appearance and counteract the yellow tint, bluing agents can therefore be used according to the invention. Furthermore, the bluing agent can be incorporated into the inventive 2025PF30041 - Abroad

[0292] - 39 -thermoplastic compositions to eliminate yellowing caused by the polymer or any UV absorber present, e.g., for optical applications such as lenses. Any bluing agent commonly used in polycarbonate compositions can be employed without particular difficulty. Generally, anthraquinone dyes are preferred because these dyes are readily available. Representative examples of specific bluing agents include the trivial names Solvent Violet 13 [CI No. (Color Index No.) 60725], Solvent Violet 31 [CI No. 68210], Solvent Violet 33 [CI No. 60725], Solvent Blue 94 [CI No. 61500], Solvent Violet 36 [CI No. 68210], Solvent Blue 97 ["Macrolex Violet RR", manufactured by Lanxess], and Solvent Blue 45 [CI No. 61110], These bluing agents can be used individually or in combination with two or more.These bluing agents can be used in a quantity of generally 0.1 * 10". 5 up to 2* 10" 4 Mass parts are incorporated, with the mass parts each referring to 100 mass parts of component (I).

[0293] Antioxidants (Ild)

[0294] Furthermore, the thermoplastic composition according to the invention can contain an antioxidant. It is known to those skilled in the art that antioxidants are also frequently referred to as thermostabilizers.

[0295] Preferably, the antioxidant is selected from sterically hindered phenols, a phosphorus-containing antioxidant and a sulfur-containing antioxidant.

[0296] Sterically hindered phenols are known as antioxidants in polycarbonate chemistry. Preferably, these are compounds of the general structure (7a) or (7b).

[0297]

[0298] (7a), (7b),

[0299] where n means 1, 2, 3 or 4,

[0300] Ri, R2 and R3 each independently represent Ci to C4 alkyl or hydrogen, X represents a direct bond or an organic residue with Ci to Ceo- and the organic residue may contain oxygen and / or nitrogen,

[0301] R4 represents a direct bond, carbon, Ci-Cs alkyl, aryl or a structure according to formula (8a), (8b) or (8c). 2025PF30041 - Abroad

[0302] - 40 -

[0303]

[0304] The component C is particularly preferred if it is selected from at least one compound according to structures (9), (10), (11) and (12).

[0305]

[0306] (12).

[0307] Compound (9) is classified as CAS: 6683-19-8 and is commercially available under the name ADK Stab AO-60 from Adeka (Japan); compound (10) is classified as CAS: 85-60-9 and is commercially available under the name Songnox 4425 from Songwon Industrial Group (South Korea); compound (11) is classified as CAS: 23128-74 and is commercially available under the name Songnox 1098 from Songwon Industrial Group (2025PF30041 - Abroad).

[0308] - 41 - Group (South Korea) is available and compound (12) is classified as CAS: 36443-68-2 and is commercially available under the name Irganox 245 from BASF SE (Germany). Further preferred sterically hindered phenols are compounds of formulas (31), (32), (33) or (34).

[0309]

[0310] 2025PF30041 - Abroad

[0311] - 42 -

[0312]

[0313] (34)

[0314] The compound of formula (31) is classified as CAS: 2082-79-3 and is commercially available under the name Irganox 1076 from BASF SE (Germany). The compound of formula (32) is classified as CAS: 6683-19-8 and is commercially available under the name Irganox 1010 from BASF SE (Germany). The compound of formula (33) is classified as CAS: 35074-77-2 and is commercially available under the name Irganox 259 from BASF SE (Germany). The compound of formula (34) is classified as CAS: 1709-70-2 and is commercially available under the name ADK Stab AO 330.

[0315] The antioxidant may also be a sulfur-containing antioxidant. A sulfur-containing antioxidant may, for example, have a structure according to RI-CH2-(S) X-CH2-R2, where x = 1 or 2 and where Ri and R2 can be the same or different and represent aromatic or aliphatic groups. Preferably, Ri and R2 are aliphatic groups, which can be linear or branched and can contain functional groups.

[0316] Examples of commercially available sulfur-containing antioxidants include dilauryl 3,3'-thiodipropionate (CAS 123-28-4), distearyl 3,3'-thiodipropionate (CAS 693-36-7), ditridecylthiodipropionate (CAS 10595-72-9); pentaerythritoltetrakis ([β-laurylthiopropionate (CAS 29598-76-3), 2,2'-thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (CAS 41484-35-9), dimyristylthiodipropionate (CAS 16545-54-3) and distearyl disulfides (CAS 2500-88-1), as well as mixtures of these substances.

[0317] Alternatively, the sulfur-containing antioxidant can comprise one or more diphenyl thioesters such as 4,4'-thiobis(2-t-butyl-5-methylphenol) (CAS 96-69-5) and 2,2'-thiobis(6-t-butyl-4-methylphenol) (CAS 90-66-4).

[0318] Pentaerythritoltetrakis ([β-laurylthiopropionate] (CAS 29598-76-3) (structure (35).2025PF30041 - Abroad) is particularly preferred

[0319] OO

[0320] H3C(H2C)H / (CH2) H CH3

[0321] 'S oos

[0322] o— -^^0

[0323] S— (CH2)nCH3(CH2) H CH3

[0324]

[0325] (35)

[0326] The antioxidant can also be a phosphorus-containing antioxidant. Preferably, this is a phosphorus(III) compound that is oxidized to phosphorus(V) compounds in the melt. Organic phosphites, phosphine compounds, and phosphonates, especially organic phosphites and phosphonates, are also preferably used.

[0327] Spezifische Beispiele für die Verbindung umfassen Triphenylphosphit, Tris(nonylphenyl)phosphit, Tris(2,4-di-tert-butylphenyl)phosphit, Tridecylphosphit, Trioctylphosphit, Trioctadecylphosphit, Didecylmonophenylphosphit, Dioctylmonophenylphosphit, Diisopropylmonophenylphosphit, Monobutyldiphenylphosphit, Monodecyldiphenylphosphit, Monooctyldiphenylphosphit, Bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritoldiphosphit, 2,2-Methylenbis(4,6-di-tert-butylphenyl)octylphosphit, Bis(nonylphenyl)pentaerythritoldiphosphit, Bis(2,4-di-tert-butylphenyl)pentaerythritoldiphosphit, Distearylpentaerythritoldiphosphit, Tributylphosphat, Triethylphosphat, Trimethylphosphat, Triphenylphosphat, Diphenylmonoorthoxenylphosphat, Dibutylphosphat, Dioctylphosphat, Diisopropylphosphat, Tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylen-diphosphinat, Dimethylbenzolphosphonat, Diethylbenzolphosphonat und Dipropylbenzolphosphonat.The phosphines that can be used include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine and tributylphosphine.

[0328] Connections according to structures (36), (37), (38), (39), (40), (41), (42) or (43) are preferred. 2025PF30041 - Foreign

[0329] - 44 -

[0330]

[0331] Compound (36) is classified as CAS: 31570-04-4 and is commercially available under the name Irgafos 168 from BASF SE (Germany). Compound (37) is classified as CAS: 237-249-1 and is commercially available under the name Brüggolen H10 from Brüggeman (Germany). Compound (38) is classified as CAS: 26741-53-7 and is commercially available under the name Irgafos 126 from BASF SE2025PF30041 - Abroad

[0332] (Germany). Compound (39) is classified as CAS: 603-35-0 and is commercially available under the name Triphenylphosphine from BASF SE (Germany). Compound (40) is classified as CAS: 80693-00-1 and is commercially available under the name ADK Stab PEP 36 from Adeka (Japan). Compound (41) is classified as CAS: 126050-54-2 and is commercially available under the name ADK Stab HP-10 from Adeka (Japan). Compound (42) is classified as CAS: 26523-78-4 and is commercially available under the name ADK Stab 1178 from Adeka (Japan). Compound (43) is classified as CAS: 512-56-1 and is known as trimethyl phosphate. These phosphorus compounds can be used individually or in combination with two or more of them.

[0333] Another suitable antioxidant containing phosphorus(III) is AddWorks LXR 568 MP from Clariant (Switzerland). This compound is also known as Irgafos PEP-Q and has the formula (44).

[0334]

[0335] (44).

[0336] Ganz besonders bevorzugt sind Pentaerythritoltetrakis(3-mercaptopropionat), Pentaerythritoltetrakis(3-laurylthiopropionat), Glycerol-3 -stearylthiopropionat, Triethylenglykol-bis [3 -(3 -tert-butyl-5 -methyl -4-hydroxyphenyl)propionat] , 1,6-Hexandiol-bis [3 -(3 ,5 -di-tert-butyl-4-hydroxyphenyl)propionat] , Pentaerythritoltetrakis [3 -(3 ,5 -di-tert-butyl-4-hydroxyphenyl)propionat], Octadecyl-3 -(3,5-di-tert-butyl-4-hydroxyphenyl)propionat, l,3,5-Trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzol, N,N-Hexamethylenbis(3,5-di-tert-butyl-4-hydroxyhydrozimtsäureamid), 3,5-Di-tert-butyl-4-hydroxybenzylphosphonat-diethylester, Tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurat, Tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylen-diphosphinat und 3,9-Bis{l,l-dimethyl-2-[ß-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro(5,5)undecan.2025PF30041 - Ausland

[0337] - 46 - Such an antioxidant is preferably added to the thermoplastic composition according to the invention in an amount of 0 to 1 parts by mass, particularly preferably 0.001 to 1 parts by mass, more preferably 0.01 to 0.5 parts by mass, and even more preferably 0.02 to 0.3 parts by mass, wherein the parts by mass are each based on 100 parts by mass of component (I). Too low an amount of the antioxidant may result in insufficient anti-discoloration protection during molding. If the amount of the antioxidant is too high, the composition may lead to increased mold deposits during injection molding or increased roller deposits during film extrusion, which impairs the surface appearance of the product.

[0338] Lubricating and demolding agents (Ile)

[0339] The inventive composition may contain at least one lubricant and demolding agent (Ile) selected from the group consisting of fatty acids with 10 to 30 carbon atoms, their fatty acid esters of mono- or polyhydric alcohols, natural animal waxes, natural vegetable waxes, natural petroleum-based waxes, montan waxes, olefin waxes, silicone oils, and organopolysiloxanes. Lubricants and demolding agents can further improve mold release, e.g., in the injection molding process.

[0340] Fatty acid esters of monohydric or polyhydric alcohols can be used as lubricants and demolding agents. Examples of monohydric alcohols include stearyl alcohol, palmitic alcohol, and Guerbet alcohols. Examples of dihydric alcohols are glycol; trihydric alcohols include glycerol; tetrahydric alcohols include pentaerythritol and mesoerythritol; pentahydric alcohols include arabitol, ribitol, and xylitol; hexahydric alcohols include mannitol, glucite (sorbitol), and dulcite.

[0341] Beeswax, camauba wax or paraffin wax can also be used, for example.

[0342] The higher molecular weight fatty acids are preferably saturated fatty acids with 10-30 carbon atoms. Examples of such saturated fatty acids are myristic acid, lauric acid, palmitic acid, stearic acid, and behenic acid.

[0343] The higher molecular weight fatty acid esters are preferably partial or complete esters (monoesters, diesters, triesters, tetraesters, pentaesters and hexaesters or mixtures thereof, in particular statistical mixtures, of saturated, aliphatic C10 to C36 monocarboxylic acids and optionally hydroxy monocarboxylic acids) of mono- or polyhydric alcohols with 1-20 carbon atoms with saturated fatty acids with 10-362025PF30041 - Abroad

[0344] - 47 - carbon atoms. Examples of partial or complete esters of mono- or polyhydric alcohols with saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbitol, stearyl stearate, behenic acid monoglyceride, behenyl behenate, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargoneate, propylene glycol monostearate, palmityl palmitate, butyl stearate, methyl laureate, isopropyl palmitate, sorbitan monostearate, and 2-ethylhexyl stearate. Of these, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and behenyl behenate are preferred.

[0345] Commercially available fatty acid esters, especially of pentaerythritol and glycerol, may contain < 60% different partial esters due to manufacturing processes.

[0346] These sliding and demolding agents can be used individually or as a mixture of two or more.

[0347] Esters of dihydric alcohols, especially ethyl glycol, are particularly preferred. These include, for example, substances under CAS No. 91031-31-1 (C16 to C18 esters of ethylene glycol). Trade names include Loxiol 895 and Loxiol 897. These esters can reduce or prevent molecular weight degradation during processing, such as injection molding, and thus facilitate processing.

[0348] The content of the sliding and demolding agent in the thermoplastic composition according to the invention is preferably 0 to 2 parts by mass, particularly preferably 0.0001 to 2 parts by mass, where the parts by mass are based on 100 parts by mass of component (I). Particularly preferably, the sliding and demolding agent is used in a proportion of 0.01 to 1.5 parts by mass, and most preferably between 0.1 and 1 parts by mass.

[0349] Acid-containing additive (Ilf)

[0350] The thermoplastic composition according to the invention may furthermore contain at least one acid-containing additive. This includes, for example, free acids, but also compounds that release acids, such as trialkyl phosphates.

[0351] The addition of the at least one acid-containing additive preferably takes place after completion of the polycondensation of the copoly(ester) carbonate. The acid-containing additive primarily serves to neutralize alkaline components, especially polycondensation catalysts.

[0352] Examples of acid-containing additives include Brønsted acids and their esters, such as hydrochloric acid, nitric acid, boric acid, sulfuric acid, sulfurous acid, phosphoric acid, 2025PF30041 - Abroad

[0353] Phosphorous acid, hypophosphoric acid, polyphosphoric acid, adipic acid, ascorbic acid, aspartic acid, azelaic acid, benzoic acid, formic acid, valeric acid, citric acid, glycolic acid, glutamic acid, glutaric acid, cinnamic acid, mesoticic acid, acetic acid, tartaric acid, oxalic acid, p-toluenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, nicotinic acid, picric acid, picolinic acid, phthalic acid, terephthalic acid, propionic acid, benzenesulfonic acid, benzenesulfonic acid, malonic acid, and maleic acid. Among these acidic compounds or their derivatives, sulfonic acids or their esters are preferred. p-Toluenesulfonic acid, methyl p-toluenesulfonate, and butyl p-toluenesulfonate are particularly preferred. The addition of a free acid as an acid-containing additive is especially preferred.

[0354] Equally preferred, one or more sulfonic acid esters may be used, which are selected from the group consisting of sulfonic acid esters of formulas (B1), (B2), (B3), (B4), (B5), (B6), (B7), (B8)

[0355]

[0356] (B7) (B8> in which

[0357] m independently stands for 0 or 1,

[0358] n independently represents an integer from 0 to 8,

[0359] q represents an integer from 0 to 10,

[0360] RI independently stands for hydrogen or for unsubstituted or halogen-substituted Ci- to C2o-alkyl, 2025PF30041 Abroad

[0361] - 49 - R2 and R3 independently of each other for hydrogen or for Ci- to Ce-alkyl, C4- to Cso-alkylcarboxyl or for the rest of the formula (bl)

[0362]

[0363] stand,

[0364] where in formula (bl) RI and n have the meaning mentioned above,

[0365] R4 stands for C4- to Cso-alkylcarboxyl or for the rest of the formula (bl),

[0366] R5 and R6 independently represent hydrogen or unsubstituted or halogen-substituted Ci- to C2o-alkyl and

[0367] RI 1 independently represents hydrogen or di-(Ci- to C4)-alkylamino.

[0368] Sulfonic acid esters of formulas (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI), (XII) are particularly preferred: 2025PF30041 - Abroad

[0369] - 50 -

[0370] (VIII)

[0371]

[0372] (VII)

[0373] (XII)

[0374] Trialkyl phosphates can also be used as acid-containing additives. The trialkyl phosphates most preferably have the following structure: (50)2025PF30041 - Abroad

[0375] - 51 -

[0376]

[0377] OR 22 ( 50)

[0378] where R21 to R23 can be H, identical or different linear, branched, or cyclic alkyl groups. C1-C18 alkyl groups are particularly preferred. Cl-C18-alkyl, for example, represents methyl, ethyl, n-propyl, isopropyl, n-butyl, n-butyl, tert-butyl, etc. -Butyl, n-pentyl, 1 -methylbutyl, 2-methylbutyl, 3 -methylbutyl, neo-pentyl, 1 -ethylpropyl, cyclohexyl, cyclopentyl, n-hexyl, 1,1 -dimethylpropyl, 1,2-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3 -Methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-Ethyl-1-methylpropyl, 1-Ethyl-2-methylpropyl or 1-Ethyl-2-methylpropyl, n-heptyl and n-octyl, pinakyl, adamantyl, the isomeric menthyls, n-nonyl, n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

[0379] Particularly suitable alkyl phosphates include, for example, mono-, di- and trihexyl phosphate, triisoctyl phosphate and trinonyl phosphate.

[0380] Triisooctyl phosphate (tris-2-ethylhexyl phosphate) is preferably used as the alkyl phosphate. Mixtures of various mono-, di-, and trialkyl phosphates can also be used.

[0381] The thermoplastic composition according to the invention preferably comprises 0 to 0.1 parts by mass, more preferably 0.00001 to 0.1 parts by mass, more preferably 0.00005 to 0.01 parts by mass, and even more preferably 0.0001 to 0.001 parts by mass of the at least one acidic additive, wherein the parts by mass are each based on 100 parts by mass of component (I). The acidic additive is particularly preferably a phosphorus-containing compound, and the amount of this phosphorus-containing compound is 0.0001 to 1 part by mass, more preferably 0.0005 to 0.1 parts by mass, and even more preferably 0.001 to 0.05 parts by mass. Insufficient amounts of the acidic additive may result in the discoloration of the thermoplastic composition according to the invention not being adequately inhibited during injection molding under conditions with prolonged residence time of the composition. Furthermore, the molecular weight may decrease.Excessive amounts of the acid-containing additive can lead to a significantly reduced hydrolytic resistance in the thermoplastic composition according to the invention. Furthermore, an excessive amount of the acid-containing additive can also lead to a reduction in molecular weight. 2025PF30041 - Foreign.

[0382] - 52 -

[0383] OH and acid group scavengers (Ilg)

[0384] Likewise, the thermoplastic composition according to the invention can contain at least one OH and acid group scavenger. Preferably, the OH and acid group scavenger is a compound containing an epoxy group or a carbodiimide group.

[0385] Alkaline compound (Ilh)

[0386] Likewise, the thermoplastic composition according to the invention can comprise at least one alkaline compound.

[0387] The copoly(ester) carbonate used according to the invention contains isosorbide. It is known that isosorbide tends to be oxidized by oxygen; this is particularly the case under thermal stress. Traces of moisture can contribute to the cleavage of the bicyclic system. The oxidation of isosorbide produces decomposition products, such as products with more than two OH groups and possibly formic acid and sorbitol components or sorbitol derivatives. Furthermore, oxidation products such as furan derivatives may be present. If isosorbide containing these decomposition products is used, for example, to produce a copoly(ester) carbonate, these decomposition products cause discoloration of the resulting polymer or a significant deterioration of its properties.Polycondensation can be negatively affected to such an extent that the target molecular weights are not achieved, gel bodies form, or the color increases significantly and the transmission decreases. In principle, OH and acid scavenger groups are added to the granules to prevent the formation of formic acid, sorbitol, or furan derivatives. However, these can themselves have negative consequences for the quality of the polycondensate, such as discoloration.

[0388] Preferably, an alkali metal salt such as sodium hydroxide is used as an OH and acid group scavenger. Such an alkali metal also acts as a polycondensation catalyst and can therefore be used even during the polycondensation of the copoly(ester) carbonate used according to the invention. However, it is undesirable to add such alkali metal salts excessively, as excessive addition makes it impossible to control the polycondensation reaction.

[0389] Preferably, the thermoplastic composition according to the invention contains 0 to V IO 3 Bulk parts, especially preferably 0.1 x IO 7 up to 1 x 10 3 Mass parts of the alkaline compound, where the mass parts are each based on 100 mass parts of component (I).2025PF30041 - Abroad

[0390] - 53 - Reducing agent (Ili)

[0391] Likewise, the thermoplastic composition according to the invention can comprise at least one reducing agent. The reducing agent is used for the same purpose as the alkaline compound (Ilh). Sodium borohydride or lithium borohydride is preferred as the reducing agent.

[0392] Preferably, the thermoplastic composition according to the invention contains 0 to V IO 3 Bulk parts, especially preferably 0.1 x IO 7 up to 1 x | () parts by mass of the reducing agent, where the parts by mass are each based on 100 parts by mass of component (I).

[0393] Antistatic agent (Ilj)

[0394] Furthermore, the thermoplastic composition according to the invention can contain at least one antistatic agent selected from the group consisting of polyetheresteramides, glycerol monostearate, ammonium salts of dodecylbenzenesulfonic acid, phosphonium salts of dodecylbenzenesulfonic acid, quaternary ammonium salts of a perfluoroalkylsulfonic acid, maleic anhydride monoglyceride and maleic anhydride diglyceride.

[0395] Preferably, the thermoplastic composition according to the invention contains 0 to 2 parts by mass, particularly preferably 0.001 to 2 parts by mass and most preferably 0.1 to 1 parts by mass of the antistatic agent, wherein the parts by mass are each based on 100 parts by mass of component (I).

[0396] Colorant (Ilk)

[0397] Furthermore, the thermoplastic composition according to the invention can comprise at least one colorant selected from the group of inorganic pigments, which include carbon black, titanium oxide, zinc white, iron oxide red, chromium oxide, iron black, titanium yellow, zinc-iron brown, copper-chromium black, copper-iron black and oxide-based pigments, organic pigments and organic dyes, which include phthalocyanine dyes and pigments; condensed polycycles such as azo, thioindigo, perinone, perylene, quinacridone, dioxazine, isoindolinone and quinophthalone dyes and pigments, anthraquinone, perinone, perylene, methine, quinoline, heterocycle and methyl-based dyes and pigments.

[0398] Polycarbonate-containing compositions are typically dyed deep black. In this case, the improvement in the lightfastness of the polycarbonate resin composition and its molded part becomes particularly noticeable. That is to say, with 2025PF30041 - Abroad

[0399] - 54 - With a conventional deep black resin composition and a molded part produced therefrom, the deterioration of weather resistance is often manifested in the form of a defective appearance (for example, by cracking or whitish clouding). On the other hand, as described above, the thermoplastic compositions according to the invention exhibit excellent weather resistance. However, even with deep black coloring, defects in appearance such as cracking and whitish clouding can occur, which must be suppressed.

[0400] The listed dyes and pigments can be used individually or in combination of two or more. It is also possible to use an inorganic pigment and an organic dye / pigment together.

[0401] For deep black applications, it is advantageous if the composition colored with the deep black pigment and the resulting molded part have a brightness L* of 0.5 to 3. In this case, a deep black molded part with excellent design quality can be achieved. The brightness L* can be adjusted within the aforementioned range by appropriately modifying the type, combination, and quantity of the various pigments mentioned above.

[0402] To achieve a transparent or opaque color impression, the total amount of colorant is preferably between 0.001 and 5 parts by mass, where the parts by mass are based on 100 parts by mass of component (I). The lower limit of the total amount of colorant is more preferably 0.002 parts by mass and particularly preferably 0.01 parts by mass. The upper limit of the total amount of colorant is more preferably 3 parts by mass, and most preferably 2 parts by mass.

[0403] Inorganic filler (III)

[0404] The thermoplastic composition according to the invention may further contain at least one inorganic filler.

[0405] Preferably, the inorganic filler is selected from the group consisting of glass fibers, ground glass fibers, glass flakes, glass beads, carbon fiber, silica, aluminum oxide, titanium oxide, calcium sulfate powder, gypsum, gypsum whiskers, barium sulfate, talc, mica, calcium silicate such as wollastonite, carbon black, graphite, iron powder, copper powder, molybdenum disulfide, silicon carbide, silicon carbide fiber, silicon nitride, silicon nitride fiber, brass fiber, stainless steel fiber, potassium titanate fiber and whiskers.

[0406] Particularly preferred are fibrous glass fillers, powdered glass fillers and flaky glass fillers; fibrous carbon fillers, powdered carbon fillers and flaky carbon fillers; as well as various types. 2025PF30041 - Foreign

[0407] - 55 -of whiskem, mica, and talc. Particularly preferred examples include glass fibers, glass flakes, ground glass fibers, carbon fiber, wollastonite, mica, and talc. Of these inorganic fillers, any glass fibers or ground glass fibers used in thermoplastic resins may be employed. In particular, alkali-free glass (E-glass) is preferred. The glass fibers preferably have a diameter of 6 pm to 20 pm, more preferably of 9 pm to 14 pm. If the diameter of the glass fibers is too small, the reinforcing effect tends to be insufficient. If the diameter of the glass fibers is too large, they tend to negatively affect the appearance of the product.

[0408] Preferred examples of glass fibers include cut rovings, preferably cut to a length of 1 mm to 6 mm, and commercially available ground glass fibers, preferably in a ground form with a length of 0.01 mm to 0.5 mm. These two types of glass fibers can be used individually or as a mixture. The glass fibers to be used in the invention can be subjected, prior to use, to a surface treatment with, for example, a silane coupling agent such as an aminosilane or epoxysilane to improve adhesion to the copoly(ester) carbonate used in the invention, or to a sizing treatment with an acrylic resin, urethane resin, or the like to improve handling.

[0409] Any glass beads commonly used with thermoplastic resins can be used. Alkali-free glass (E-glass) is preferred. Regarding the shape of the glass beads, a spherical shape with a diameter of 10 pm to 50 pm is preferred.

[0410] Examples of glass flakes include scale-like glass flakes. The glass flakes incorporated into the copoly(ester) carbonate used according to the invention can have a maximum diameter of generally 1,000 pm or less, preferably 1 pm to 500 pm, and an aspect ratio (ratio of maximum diameter to thickness) of 5 or greater, preferably 10 or greater, particularly preferably 30 or greater.

[0411] The carbon fibers are not particularly restricted, and examples include various types of carbon fibers, such as flame-resistant fibers, carbon-containing fibers, and graphite fibers, produced by combustion from raw materials such as acrylic fibers, petroleum- or coal-based specialty pitches, cellulose fibers, and lignin. Such carbon fibers have an average aspect ratio (fiber length / fiber diameter) of preferably 10 or greater, and particularly preferably 50 or greater. If the average aspect ratio of the carbon fibers is too low, the polycarbonate resin composition tends to have reduced electrical conductivity.

[0412] - 56 - Strength and stiffness. The carbon fibers can have a diameter of 3 pm to 15 pm and can be used in any form, such as cut rovings, roving strands, or milled fibers, to achieve the desired aspect ratio. Carbon fibers of one type or a mixture of two or more types of carbon fiber can be used.

[0413] The carbon fibers can be subjected to a surface treatment such as an epoxy treatment, urethane treatment or oxidation treatment to increase the affinity to the copoly(ester) carbonate used according to the invention, provided that the surface treatment does not impair the properties of the thermoplastic composition according to the invention.

[0414] The timing of adding an inorganic filler to copoly(ester) carbonate and the methods for its addition are not particularly restricted. Examples of the timing of addition include the following: When producing copoly(ester) carbonate by a transesterification process, the filler can be added at the point of completion of the polymerization reaction. Other examples of the timing of addition, regardless of the polymerization process, include: the point in time when the copoly(ester) carbonate is in a molten state, such as when kneading the copoly(ester) carbonate together with other additives; and the point in time when the copoly(ester) carbonate is mixed / kneaded in a solid state, e.g., in the form of pellets or powder, using an extruder or similar device.Examples of addition methods include: a method in which the inorganic filler is directly mixed or kneaded with the copoly(ester) carbonate; and a method in which the inorganic filler is added as a highly concentrated masterbatch prepared using the inorganic filler and a small amount of the copoly(ester) carbonate, another resin, etc.

[0415] The thermoplastic composition according to the invention preferably contains the inorganic filler in an amount of 0 to 100 parts by mass, preferably 1 to 100 parts by mass, and particularly preferably 3 to 50 parts by mass, wherein the parts by mass are each based on 100 parts by mass of component (I). Too small an amount of the inorganic filler leads to an insufficient reinforcing effect. Too large an amount tends to impair the appearance.

[0416] Flame retardant (Ilm)

[0417] The thermoplastic composition according to the invention can further comprise at least one flame retardant selected from the group consisting of phosphorus compounds-2025PF30041 - Abroad

[0418] - 57-based, halogen compound-based, metal sulfonate-based and silicon compound-based flame retardants are included.

[0419] Preferred examples of phosphorus compound-based flame retardants include phosphoric acid ester compounds, phosphazene compounds, red phosphorus, coated red phosphorus, and polyphosphate compounds. The amount of such a phosphorus compound-based flame retardant is preferably 0.1 to 20 parts by weight per 100 parts by weight of component (I). If the amount of flame retardant incorporated is too low, it is difficult to achieve sufficient flame retardancy. If the amount is too high, the heat resistance may be adversely affected. Preferred phosphoric acid ester compounds are those of the general formula (50):

[0420]

[0421] (50)

[0422] wherein

[0423] R 1 , R 2 , R 3 and R 4, each optionally halogenated Ci to Cs-alkyl, each optionally by alkyl, preferably Ci to C4-alkyl, and / or halogen, preferably chlorine, bromine, substituted Cs to Ce-cycloalkyl, Ce to C2o-aryl or C? to Cn-aralkyl, independently of each other

[0424] n independently of each other, 0 or 1

[0425] q 0 to 30 and

[0426] X can represent a mono- or polycephalic aromatic residue with 6 to 30 C atoms, or a linear or branched aliphatic residue with 2 to 30 C atoms, which may be OH-substituted and contain up to 8 ether bonds.

[0427] R are preferred 1 , R 2 , R 3 and R 4 independently for Ci to C4-alkyl, phenyl, naphthyl, or phenyl-Ci-C4-alkyl. The aromatic groups R 1 , R 2 , R 3 and R 4These compounds can in turn be substituted with halogen and / or alkyl groups, preferably chlorine, bromine, and / or Ci to C4 alkyl. Particularly preferred aryl groups are cresyl, phenyl, xylenyl, propylphenyl, or butylphenyl, as well as the corresponding brominated and chlorinated derivatives thereof.

[0428] X in formula (50) preferably represents a mono- or polycephalic aromatic residue with 6 to 30 carbon atoms. This is preferably derived from diphenols. 2025PF30041 - Abroad

[0429] - 58 -n in formula (50) can be 0 or 1 independently, preferably n is equal to 1.

[0430] q represents values ​​from 0 to 30. When using mixtures of different components of formula (50), mixtures may preferably have number-averaged q values ​​of 0.3 to 10, particularly preferably 0.5 to 10, and especially 1.05 to 1.4.

[0431] X is particularly preferred for

[0432]

[0433] or their chlorinated or brominated derivatives, in particular X is derived from resorcinol, hydroquinone, bisphenol A or diphenylphenol. X is particularly preferably derived from bisphenol A.

[0434] Monophosphates (q=0), oligophosphates (q=1-30) or mixtures of mono- and oligophosphates can be used as flame retardants.

[0435] Monophosphorus compounds of formula (50) include in particular tributyl phosphate, tris-(2-chloroethyl) phosphate, tris-(2,3-dibromoprobyl) phosphate, tri-(2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, diphenylcresyl phosphate, diphenyloctyl phosphate, diphenyl-2-ethylcresyl phosphate, tri-(isopropylphenyl) phosphate, halogen-substituted aryl phosphates, dimethyl methylphosphonic acid ester, diphenyl methylphosphenic acid ester, diethyl phenylphosphonic acid ester, triphenylphosphine oxide or tricresylphosphine oxide.

[0436] A preferred flame retardant is bisphenol-A based oligophosphate according to formula (51).

[0437]

[0438] The phosphorus compounds according to formula (50) are known (see e.g. EP-A 363 608, EP-A 640 655) or can be prepared analogously using known methods (e.g. B2025PF30041 - Foreign

[0439] Ullmann's Encyclopedia of Technical Chemistry, Vol. 18, pp. 301 ff. 1979; Houben-Weyl, Methods of Organic Chemistry, Vol. 12 / 1, p. 43; Beilstein Vol. 6, p. 177).

[0440] The mean q values ​​can be determined by determining the composition of the phosphate mixture (molecular weight distribution) using a suitable method (gas chromatography (GC), high pressure liquid chromatography (HPLC), gel permeation chromatography (GPC)) and calculating the mean values ​​for q from this.

[0441] Alternatively, phosphazenes according to formula (52) or (53) are particularly preferred as flame retardants:

[0442] R — P=N

[0443] (52),

[0444]

[0445] (53),

[0446] wherein

[0447] R is the same or different in each case and represents amino, optionally halogenated, preferably fluorine-halogenated Ci to Cs-alkyl, or Ci to Cs-alkoxy, optionally substituted by alkyl, preferably Ci to C4-alkyl, and / or halogen, preferably chlorine and / or bromine, Cs to Ce-cycloalkyl, Ce to C2o-aryl, preferably phenyl or naphthyl, Ce to C2o-aryloxy, preferably phenoxy, naphthyloxy, or C? to Cn-aralkyl, preferably phenyl-Ci-C4-alkyl,

[0448] k stands for 0 or a number from 1 to 15, preferably a number from 1 to 10.

[0449] Examples include propoxyphosphazene, phenoxyphosphazene, methylphenoxyphosphazene, aminophosphazene, and fluoroalkylphosphazenes. Phenoxyphosphazene is preferred. The phosphazenes can be used alone or as a mixture. The R group can always be the same, or two or more groups in formulas (52) and (53) can be different. 2025PF30041 - Abroad

[0450] - 60 - Phosphazenes and their preparation are described, for example, in EP-A 728 811, DE-A 1 961668 and WO 97 / 40092.

[0451] Examples of halogen compound-based flame retardants include tetrabromobisphenol A, tribromophenol, brominated aromatic triazines, tetrabromobisphenol A epoxy oligomers, tetrabromobisphenol A epoxy polymers, decabromodiphenyl oxide, tribromolyl ether, tetrabromobisphenol A carbonate oligomers, ethylenebistetrabromomphtalimide, decabromodiphenylethane, brominated polystyrene, and hexabromocyclododecane.

[0452] The amount of such a halogen-based flame retardant can range from 0.1 to 20 parts by mass per 100 parts by mass of component (I). If the amount of halogen-based flame retardant incorporated is too low, it is difficult to achieve sufficient flame retardancy. If the amount is too high, the composition not only has reduced mechanical strength, but discoloration due to leaching of the flame retardant can also occur.

[0453] Examples of metal sulfonate-based flame retardants include metal salts of aliphatic sulfonic acids, metal salts of aromatic sulfonic acids, and metal salts of perfluoroalkanesulfonic acids. Preferred examples of the metals in these metal salts include Group 1 and Group 2 metals of the periodic table. Specific examples are alkali metals such as lithium, sodium, potassium, rubidium, and cesium; alkaline earth metals such as calcium, strontium, and barium; as well as beryllium and magnesium.

[0454] Of the metal sulfonate-based flame retardants, metal salts of aromatic sulfonic acids, metal salts of perfluoroalkanesulfonic acids, and the like are preferred from the perspectives of flame retardancy and thermal stability. Preferred metal salts of aromatic sulfonic acids are alkali metal salts of aromatic sulfonic acids and alkaline earth metal salts of aromatic sulfonic acids. These salts may be polymers. Specific examples of the metal salts of aromatic sulfonic acids include the sodium salt of (diphenylsulfone)-3-sulfonic acid, the potassium salt of (diphenylsulfone)-3-sulfonic acid, the sodium salt of (4,4'-dibromodiphenylsulfone)-3-sulfonic acid, the potassium salt of (4,4'-dibromodiphenylsulfone)-3-sulfonic acid, the calcium salt of (4-chloro-4'-nitrodiphenylsulfone)-3-sulfonic acid, the disodium salt of (diphenylsulfone)-3,3'-disulfonic acid, and the dipotassium salt of (diphenylsulfone)-3,3'-disulfonic acid.

[0455] Preferred metal salts of perfluoroalkanesulfonic acids are alkali metal salts of perfluoroalkanesulfonic acids, alkaline earth metal salts of perfluoroalkanesulfonic acids, and the like. Alkali metal sulfonates with a perfluoroalkyl group having 4-8 carbon atoms, alkaline earth metal sulfonates with a perfluoroalkyl group having 4-8 carbon atoms, and the like are particularly preferred. 2025PF30041 - Foreign

[0456] - 61 - Specific examples of the metal salts of perfluoroalkanesulfonic acids include sodium perfluorobutanesulfonate, potassium perfluorobutanesulfonate, sodium perfluoromethylbutanesulfonate, potassium perfluoromethylbutanesulfonate, sodium perfluorooctanesulfonate, potassium perfluorooctanesulfonate and tetraethylammonium perfluorobutanesulfonate.

[0457] The amount of such a metal sulfonate-based flame retardant is preferably 0 to 5 parts by mass, and particularly preferably 0.01 to 5 parts by mass, based on 100 parts by mass of component (I). If the amount of the incorporated metal sulfonate-based flame retardant is too low, it is difficult to achieve sufficient flame retardancy. Excessive amounts tend to lead to reduced thermal stability.

[0458] Examples of silicon compound-based flame retardants include silicone resins with silicon-bonded substituents including aromatic hydrocarbon groups and aliphatic hydrocarbon groups with 2 or more carbon atoms, silicone compounds with a branched main chain structure and organic functional groups including an aromatic group, silicone powders composed of silica particles with a polydiorganosiloxane polymer, which may have a functional group, deposited on their surface, and organopolysiloxane / polycarbonate copolymers.

[0459] Examples of silicones also include solvent-based silicone resins with a relatively low molecular weight, consisting mainly of a functional unit [R^SiO] and a trifunctional unit [RSiOi.s], and may contain a monofunctional unit [RsSiOo.s] and / or a tetrafunctional unit [SiCE]. The symbol R represents a hydrocarbon group with 1-12 carbon atoms or a hydrocarbon group with 1-12 carbon atoms substituted with one or more substituents. Examples of substituents include an epoxy group, an amino group, a hydroxyl group, and a vinyl group. By changing the type of R, compatibility with the matrix resin can be improved.

[0460] The amount of such a silicon compound-based flame retardant is preferably 0.1 to 10 parts by mass per 100 parts by mass of component (I). If the amount of silicon compound-based flame retardant incorporated is too low, it is difficult to achieve sufficient flame retardancy. Excessive amounts tend to lead to reduced heat resistance.

[0461] In this embodiment, it is preferable to use a flame retardant in combination with polytetrafluoroethylene (see also component (Iln), comprising fluoropolymers) to prevent dripping (prevent dripping or burning dripping in case of fire) in order to achieve higher flame retardancy. Polytetrafluoroethylene for 2025PF30041 - Abroad

[0462] - 62 - Droplet prevention disperses easily in polymers and tends to bind polymer molecules together to form a fibrous material.

[0463] The amount of flame retardant to be incorporated is selected according to the type of flame retardant and the desired degree of flame resistance. Generally and preferably, the thermoplastic composition according to the invention comprises a flame retardant in the range of 0 to 30 parts by mass, preferably 0.01 to 30 parts by mass, and particularly preferably 0.02 to 25 parts by mass, wherein the parts by mass are each based on 100 parts by mass of component (I). Depending on the selection of the specific flame retardant, the amounts specified above are preferred.

[0464] Polymer blend partners (Iln)

[0465] The thermoplastic composition according to the invention can include a polymeric blend partner selected from the group consisting of poly(lactic acid), poly(cyclohexanedimethanol-cyclohexanedicarboxylate), poly(propylene terephthalate), polycarbonates, polyamide 46, polyamide 12, semi-aromatic polyamides, rubber-modified graft polymers, vinyl (co)polymers selected from the group of (co)polymers made up of

[0466] B.1 50 to 99 wt.%, preferably 65 to 85 wt.%, particularly preferably 70 to 80 wt.% based on the (co)polymer of at least one monomer selected from the group of vinyl aromatics, keme-substituted vinyl aromatics and (meth)acrylic acid (Cl-C8) alkyl esters and

[0467] B.2 1 to 50 wt.%, preferably 15 to 35 wt.%, particularly preferably 20 to 30 wt.% based on the (co)polymer of at least one monomer selected from the group consisting of vinyl cyanides, (meth)acrylic acid (Cl-C8) alkyl esters, unsaturated carboxylic acids and derivatives of unsaturated carboxylic acids,

[0468] Polyolefins selected from the group consisting of polyethylene, ethylene copolymers, polypropylene and 4-methylpentene-1 resins, polyacetals, poly(amide-imides), poly(ethersulfones), polyimides, poly(phenylene oxide), poly(phenylene sulfide), poly(phenylsulfone), polyetheretherketone, liquid crystalline polyesters, poly(vinyl chloride) and fluorinated resins. It is understood that this polymeric blending partner (Iln) is different from the copoly(ester) carbonate used according to the invention.

[0469] It is evident to the expert that the meth)acrylic acid (Cl-C8) alkyl ester of component B.1 is different from the meth)acrylic acid (Cl-C8) alkyl ester of component B.2.

[0470] Preferred polycarbonates are aromatic polycarbonates, for example formed from various bisphenols including bisphenol A and bisphenol TMC; alicyclic 2025PF30041 - Abroad

[0471] - 63 - Polycarbonates, for example formed from alicyclic diols such as 3(4), 8(9)-bis(hydroxymethyl)tricyclo[5.2.1.02,6]decane or aliphatic polycarbonates, for example formed from heterocyclic diols, e.g. 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane.

[0472] A preferred fluoropolymer is polytetrafluoroethylene. The amount of polytetrafluoroethylene to be incorporated, particularly to prevent dripping (see above), is preferably 0.01 to 2.0 parts by mass per 100 parts by mass of component (I). If too little polytetrafluoroethylene is incorporated to prevent dripping, its effectiveness in preventing the melting and dripping of the copoly(ester) carbonate during combustion is insufficient. Excessive amounts tend to impair the appearance of the molded articles.

[0473] Preferably, the thermoplastic composition according to the invention contains 0 to 95 parts by mass, particularly preferably 5 to 95 parts by mass of the polymeric blending partner, wherein the parts by mass are each based on 100 parts by mass of component (I).

[0474] It is particularly preferred that the polymeric blend partner (Iln) is a vinyl (co)polymer, wherein the vinyl (co)polymer is selected from the group of (co)polymers B.1 and B.2. Thus, it is preferably a copolymer of at least one monomer from the group of vinyl aromatics, vinyl cyanides (unsaturated nitriles), (meth)acrylic acid (C1 to C8) alkyl esters, unsaturated carboxylic acids, and derivatives (such as anhydrides and imides) of unsaturated carboxylic acids. The (co)polymers B.1 and B.2 are resinous, thermoplastic, and rubber-free. The copolymer of B1 (styrene) and B.2 (acrylonitrile) is particularly preferred.

[0475] Such (co)polymers are known and can be produced by radical polymerization, in particular by emulsion, suspension, solution, or bulk polymerization. The (co)polymers have a weight-averaged molecular weight (M w), determined by gel permeation chromatography with GPC in tetrahydrofuran with polystyrene as standard, preferably from 50,000 to 250,000 g / mol, particularly preferably from 70,000 to 200,000 g / mol, particularly preferably from 80,000 to 160,000 g / mol. Preferably, this weight average of the molar mass (M w Determined by gel permeation chromatography in tetrahydrofuran with a polystyrene standard (preferably in accordance with DIN 55672-1:2007-08 using a polystyrene calibration). Calibration can be performed using narrowly distributed polystyrene standards (e.g., ReadyCal Kit Polystyrene low, nominal Mp 266 66,000 Da). The general method is defined by Currenta GmbH & Co. OHG under AM 2011-0623701-09D, which can be requested from Currenta at any time. Tetrahydrofuran (THF) was used as the eluent. The GPC can be performed using one or more cascaded 2025PF30041 - Abroad

[0476] - 64 -comprising commercially available GPC columns (e.g., SDV columns) for size exclusion chromatography. Detection can be performed via ultraviolet (UV) radiation and / or refractive index.

[0477] Preferably, the thermoplastic composition according to the invention is characterized in that the polymeric blend partner (Iln) is a rubber-modified graft polymer, which

[0478] B.1a 5 to 95 wt.%, preferably 20 to 92 wt.%, in particular 30 to 91 wt.%, based on the graft polymer, comprising at least one vinyl monomer on B.2a 95 to 5 wt.%, preferably 80 to 8 wt.%, in particular 70 to 9 wt.%, based on the graft polymer, one or more rubber-elastic graft bases with glass transition temperatures < -50°C, more preferably < -60°C, particularly preferably < -70°C.

[0479] Preferred rubber-based graft polymers can

[0480] B.a 5 to 95 wt.%, preferably 20 to 92 wt.%, in particular 30 to 91 wt.%, based on the graft polymer, of at least one vinyl monomer

[0481] B.2a comprising 95 to 5 wt.%, preferably 80 to 8 wt.%, in particular 70 to 9 wt.%, based on the graft polymer, one or more rubber-elastic graft bases with glass transition temperatures < -50°C, more preferably < -60°C, particularly preferably < -70°C.

[0482] 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).

[0483] The graft base B.2a generally has a mean particle size (D50 value) of 0.05 to 10.00 pm, preferably of 0.1 to 5.0 pm and particularly preferably of 0.2 to 1.5 pm.

[0484] The mean particle size D50 is the diameter above and below which 50 wt.% of the particles lie. Unless expressly described otherwise in the present invention, it is determined for all components by ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. and Z. Polymere 250 (1972), 782-1796).

[0485] The monomers B.a are preferably mixtures of

[0486] B.1.1 65 to 85 wt.%, particularly preferably 70 to 80 wt.%, further preferably 74 to 78 wt.%, in each case based on the sum of B.1.1 and B.1.2, vinyl aromatics and / or kem-substituted vinyl aromatics (such as styrene, a-2025PF30041 - Abroad

[0487] - 65 - Methylstyrene, p-methylstyrene, p-chlorostyrene) and / or (meth)acrylic acid (Cl-C8) alkyl esters, such as methyl methacrylate, ethyl methacrylate), and

[0488] B.1.2 15 to 35 wt.%, particularly preferably 20 to 30 wt.%, further preferably 22 to 26 wt.%, in each case based on the sum of B.1.1 and B.1.2, vinyl cyanides (unsaturated nitriles such as acrylonitrile and methacrylonitrile) and / or (meth)acrylic acid (Cl-C8) 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.

[0489] Preferred monomers B.1.1 are selected from at least one of the monomers styrene, α-methylstyrene, and methyl methacrylate; preferred monomers B.1.2 are selected from at least one of the monomers acrylonitrile, maleic anhydride, and methyl methacrylate. Particularly preferred monomers are B.1.1 styrene and B.1.2 acrylonitrile. Alternatively preferred monomers are B.1.1 methyl methacrylate and B.1.2 methyl methacrylate.

[0490] Suitable graft bases B.2a of graft polymers include, for example, diene rubbers, EP(D)M rubbers (i.e., those based on ethylene / propylene and possibly diene), acrylate, polyurethane, silicone, chloroprene, ethylene / vinyl acetate and acrylate-silicone composite rubbers.

[0491] Preferred graft bases B.1.2 are diene rubbers, preferably containing butadiene, or copolymers of dienes, preferably containing butadiene, and further copolymerizable vinyl monomers (e.g. according to B.1.1 and B.1.2) or mixtures of one or more of the aforementioned components.

[0492] Particularly preferred as a graft base is B.2a pure polybutadiene rubber. In another preferred embodiment, B.2a is styrene-butadiene rubber, particularly preferably styrene-butadiene block copolymer rubber.

[0493] The gel fraction of the graft base B.2a is at least 30 wt. %, preferably at least 40 wt. %, in particular at least 60 wt. %, in each case based on B.2a and measured as insoluble fraction in toluene.

[0494] The gel content of the grafting base B.2a or of the rubber-modified grafting polymers used according to the invention is determined at 25 °C in a suitable solvent as the insoluble fraction in these solvents (M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik I and II, Georg Thieme-Verlag, Stuttgart 1977).

[0495] Suitable polymers include, for example, ABS or MBS polymers, as described in DE-OS 2035 390 (=US PS 3 644574) or in DE-OS 2248242 (=GB-PS 1 409275) or in Ullmanns, Encyclopedia of Technical Chemistry, Vol. 19 (1980), pp. 280 ff. 2025PF30041 - Foreign

[0496] - 66 - The rubber-modified graft copolymers are produced by radical polymerization, e.g., by emulsion, suspension, solution, or bulk polymerization. Mixtures of graft copolymers produced by different methods can also be used.

[0497] When the rubber-modified graft polymers are produced by emulsion polymerization, these include

[0498] B. 5 to 75 wt.%, preferably 20 to 60 wt.%, particularly preferably 25 to 50 wt.%, based on the graft polymer, of at least one vinyl monomer

[0499] B.2a 95 to 25 wt.%, preferably 80 to 40 wt.%, particularly preferably 75 to 50 wt.%, based on the graft polymer, of one or more rubber-elastic graft bases with glass transition temperatures < -50°C, more preferably < -60°C, particularly preferably < -70°C.

[0500] The graft base B.2a of rubber-modified graft polymers produced by emulsion polymerization has a mean particle size (D50 value) of 0.05 to 2.00 pm, preferably of 0.1 to 1.0 pm, and particularly preferably of 0.2 to 0.5 pm. Rubber-modified graft polymers produced by emulsion polymerization have a gel content, measured in acetone as solvent, of preferably at least 30 wt.%, particularly preferably at least 60 wt.%, and further preferably at least 80 wt.%.

[0501] When the rubber-modified graft polymers are produced by suspension, solution or bulk polymerization, these include

[0502] B. 80 to 95 wt.%, preferably 84 to 92 wt.%, particularly preferably 87 to 91 wt.%, based on the graft polymer, of at least one vinyl monomer

[0503] B.2a 20 to 5 wt.%, preferably 16 to 8 wt.%, particularly preferably 13 to 9 wt.%, based on the graft polymer, of one or more rubber-elastic graft bases with glass transition temperatures < -50°C, more preferably < -60°C, particularly preferably < -70°C.

[0504] The graft base B.2a of graft polymers produced by suspension, solution or bulk polymerization has a mean particle size (D50 value) of 0.3 to 10.00 pm, preferably of 0.4 to 5.0 pm, particularly preferably of 0.5 to 1.5 pm.

[0505] Graft polymers produced by suspension, solution, or bulk polymerization have a gel content, measured in acetone as solvent, preferably of 10 to 50 wt.%, particularly preferably of 15 to 40 wt.%, and further preferably of 18 to 30 wt.%. Particularly suitable graft polymers produced by emulsion polymerization are, for example, ABS polymers, which are produced by emulsion polymerization. 2025PF30041 - Abroad

[0506] - 67 - Redox initiation with an initiator system of organic hydroperoxide and ascorbic acid according to US-P 4937285.

[0507] Other particularly suitable graft polymers produced by emulsion polymerization are MBS modifiers with a Kem shell structure.

[0508] It is preferred that the rubber-modified graft polymer additionally contains a free vinyl(co)polymer, i.e., one that is not chemically bound to the rubber base and not enclosed within the rubber particles, preferably a vinyl(co)polymer consisting of the monomers according to B.1a. This may be formed during the polymerization of the graft polymers during manufacturing (grafting onto the graft base is not always complete) or may be polymerized separately and added. It is also possible that part of the free vinyl(co)polymer originates from the graft polymers themselves during manufacturing, and another part is polymerized separately and then added.The proportion of free vinyl(co)polymer (regardless of its origin), measured as the proportion soluble in acetone, in a possible mixture of rubber-modified graft polymers and rubber-free vinyl(co)polymers is, based on this mixture, preferably at least 5 wt.%, more preferably at least 30 wt.%, and further preferably at least 50 wt.%.

[0509] The rubber-modified graft polymer is particularly favored in the form of Kem shell graft copolymers. These are especially effective impact modifiers. Examples of commercially available Kem shell graft copolymers include:

[0510] Von Dow Chemical Japan: Paraloid EXL2602, Paraloid EXL2603, Paraloid EXL2690, Paraloid EXL2691J, Paraloid EXL2650J, Paraloid EXL2655, Paraloid EXL2311, Paraloid EXL2313, Paraloid EXL2315, Paraloid KM330, Paraloid KM336P, Paraloid KCZ201; Von Mitsubishi Rayon Co., Ltd.: Metabiene C-223A, Metabiene E-901, Metabiene S-2001, Metabiene W-450A, Metabiene SRK-200; Von Kaneka Corporation: Kaneace M-210, Kaneace M-511, Kaneace M-600, Kaneace M-400, Kaneace M-580, Kaneace M-711, Kaneace MR-01.

[0511] The content of rubber-modified graft polymer in the mixture with the vinyl (co)polymer in the thermoplastic composition according to the invention is preferably 3 to 20 parts by mass per 100 parts by mass of component (I). If the upper limit of this range is exceeded, the appearance of the resulting molded part tends to deteriorate and the heat resistance decreases. If the lower limit is not met, the improvement in surface impact toughness and impact resistance becomes less pronounced. The lower limit of the content of rubber-modified graft polymer in 2025PF30041 - Foreign

[0512] - 68 - The mixture with the vinyl(co)polymer is particularly preferably 5 parts by mass. The upper limit of the content is particularly preferably 15 parts by mass.

[0513] The polymeric blend partners can be used individually or as a mixture of two or more of them, and one or more of the polymeric blend partners to be used can be appropriately selected according to the intended use, taking into account required properties such as heat resistance, chemical resistance and malleability.

[0514] The person responsible can see how the at least one polymeric blend partner can be mixed with the copoly(ester) carbonate. There are no particular restrictions regarding the methods for mixing the copoly(ester) carbonate with this polymeric blend partner and any other additives, nor regarding the timing of the mixing. For example, the polymeric blend partner can be added during the polymerization reaction or at the end of the polymerization reaction, or it can be added when the copoly(ester) carbonate is in a molten state, such as when kneading the copoly(ester) carbonate. It is also possible to mix the polymeric blend partner with the copoly(ester) carbonate in a solid state, e.g., in the form of pellets or powder, and then knead the mixture using an extruder or similar device.

[0515] Furthermore, it is evident to a person skilled in the art how the at least one additive can be added to the copoly(ester) carbonate. This can preferably be achieved by mixing the components either simultaneously or in any sequence using a mixing machine such as a gyratory mixer, twin-cylinder mixer, Nauta mixer, Banbury mixer, kneading rollers or extruder.

[0516] According to the invention, the term “comprise” is preferably to be understood as “essentially consisting of” and most preferably as “consisting of”.

[0517] The thermoplastic composition according to the invention is preferably characterized in that the composition contains at least one additive (Ila) to (Iln) in the specified amounts.

[0518] 0.05 to 10 parts by mass (Ila) of the UV absorber,

[0519] 0.001 to 5 parts by mass (Ilb) of the sterically hindered amine light stabilizer, 0.1 x 10" 5 up to 2x 10" 4Bulk parts (IIc) of the bluing agent, 2025PF30041 - Abroad

[0520] - 69 - 0.001 to 1 parts by mass (Ild) of the antioxidant,

[0521] 0.0001 to 2 parts by mass (Ile) of the sliding and demolding agent,

[0522] 0.00001 to 1 part by mass (1lf) of the acidic additive,

[0523] 0.05 to 5 parts by mass (Ilg) of the OH and acid group scavenger,

[0524] 0, 1 x IO 7 up to 1 x IO 3 Mass fractions (Ilh) of the alkaline compound,

[0525] 0, 1 x IO 7 up to 1 x IO 3 (Ili) Mass fractions of the reducing agent,

[0526] 0.001 to 2 parts by mass (Ilj) of the antistatic agent,

[0527] 0.001 to 3 parts by mass (Ilk) of the colorant,

[0528] 1 to 100 parts by mass (III) of the inorganic filler,

[0529] 0.01 to 30 parts by mass (Ilm) of the flame retardant and / or

[0530] comprises 5 to 95 parts by mass (Iln) of the polymeric blend partner,

[0531] wherein the mass parts are each based on 100 mass parts of component (I). It is particularly preferred that the thermoplastic composition according to the invention contains at least (Ild) and (Ile) as additives.

[0532] It is also preferred that the thermoplastic composition according to the invention additionally contains at least (IIc) and / or (Ilk) as an additive.

[0533] It is also preferred that the thermoplastic composition according to the invention contains at least (Ila) and / or (Ilb) as an additive in addition to (Ild) and (Ile).

[0534] It is also preferred that the thermoplastic composition according to the invention contains, in addition to (Ild) and (Ile), at least (III) and / or (Ilm) as an additive.

[0535] It is also preferred that the thermoplastic composition according to the invention contains at least (Iln) as an additive in addition to (Ild) and (Ile).

[0536] The thermoplastic composition according to the invention most preferably contains at least one additive (Ild), (Ile) and (Ilf).

[0537] The thermoplastic compositions developed according to the invention exhibit excellent properties. It has been observed that unstabilized aliphatic polycarbonates made from isosorbide tend to experience a decrease in viscosity or molecular weight during processing. This leads to a negative change in the polymer's physical properties, for example, through injection molding and / or compounding. Therefore, every thermal processing step has the potential to degrade the polymer's properties.

[0538] Polycarbonates and polyester carbonates typically have either OH or phenyl end groups. The phenyl end groups can be phenyl carbonate or, in the case of ester carbonates, phenyl ester groups. In principle, free acid groups are also possible in polyester carbonates. 2025PF30041 - International

[0539] - 70 - OH end groups, in particular, can lead to transesterification and thus reduce the molecular weight. This can occur especially in combination with moisture and residual catalyst content. OH groups can also be thermally or photochemically oxidized. This leads to colored products and is undesirable.

[0540] In the case of isosorbide, free OH groups can also lead to elimination. In principle, elimination is also possible through chain severance. Such processes are usually thermally induced and damage the polymer, as they can lead to discoloration and molecular weight degradation. According to the invention, the thermoplastic composition is preferably characterized in that the copoly(ester) carbonate (I) contains less than 8% end groups of formula (Y).

[0541]

[0542] where the position of formula (Y) marked with is the position at which the end group of formula (Y) is incorporated into the copoly(ester) carbonate and the % refers to the totality of the end groups.

[0543] In particular, it is preferred that the copoly(ester) carbonate (I) contains less than 6% and, more preferably, less than 5% of these end groups, where the percentage refers to the total number of end groups. These end groups are typically in the range of 0.0001 to 5%. In principle, such end groups can be reduced by using sufficient amounts of aryl carbonate for the polycondensation to achieve a high proportion of aryl-terminated end groups. On the other hand, the amount of aryl carbonate must not be too high, otherwise the target molecular weight cannot be achieved. Furthermore, the copoly(ester) carbonate must not be heated to temperatures above 300 °C, and more preferably not above 280 °C, during the manufacturing process and in subsequent processing steps. Preferably, the copoly(ester) carbonate contains more than 20%, and more preferably, more than 30%, of phenyl end groups.The ratio of phenyl end groups to OH end groups can be determined using ¹H-NMR.

[0544] In principle, it is possible for the isosorbide ring to cleave, resulting in a higher number of OH groups. This can lead to transesterification, chain severance, or branching. Overall, this can significantly degrade the polymer properties. The opening of the bicyclic system can be caused primarily by catalysts remaining in the polymer, such as alkaline or acidic components, as well as by oxidative processes. It is also possible, in principle, to... Sorbitol-2025PF30041 - Abroad

[0545] - 71 - Impurities may be introduced through the raw material (isosorbide). Such impurities or defects are described in US20110077377.

[0546] The phenomena mentioned above can contribute to a deterioration of the quality of the copoly(ester) carbonate. Therefore, according to the invention, it is advantageous to use at least one additive. This allows thermoplastic compositions with excellent property profiles to be provided.

[0547] Furthermore, it is possible that the polymer contains residual monomers. These may be, in particular, phenol or substituted phenol that was not completely removed during polycondensation. Phenol and other diol monomers can contribute to transesterification and molecular weight degradation. It is preferred that the polymer contains less than 0.15 wt%, preferably less than 0.1 wt%, and especially preferably less than 0.09 wt% phenol.

[0548] The compositions according to the invention can be produced, for example, by mixing the copoly(ester) carbonate and the other components in a known manner and melt-compounding and melt-extruding them at temperatures preferably 200°C to 300°C, particularly preferably 220°C to 300°C, in conventional equipment such as internal kneading machines, extruders, and twin-screw extruders. This process is generally referred to as compounding within the scope of this application. The thermoplastic molding compound according to the invention is obtained by compounding. In one aspect of the present invention, a thermoplastic molding compound is provided which is obtained from the thermoplastic composition according to the invention. In another aspect of the invention, a molded body is provided which is obtained from the thermoplastic molding compound.The molded parts according to the invention can be produced, for example, by injection molding, extrusion, and blow molding. Another processing method is the production of molded parts by deep drawing from previously manufactured sheets or films.

[0549] Description of the character

[0550] Figure 1: 'H-NMR spectrum of the copolycarbonate of the inventive example 17 in CDCE

[0551] Figure 2: 'H-NMR spectrum of the copolycarbonate of the inventive example 16 in CDCE2025PF30041 - Abroad

[0552] - 72 - Examples

[0553] Materials used:

[0554] Cyclohexanedicarboxylic acid: 1,4-Cyclohexanedicarboxylic acid; CAS 1076-97-7 99%; Tokyo Chemical Industries, Japan, abbreviated as CHDA.

[0555] Diphenyl carbonate: Diphenyl carbonate, 99.5%, CAS 102-09-0; Acros Organics, Geel, Belgium, abbreviated as DPC

[0556] 4-Dimethylaminopyridine: 4-(Dimethylaminopyridine; >98.0%; purum; CAS 1122-58-3; Sigma-Aldrich, Munich, Germany, abbreviated as DMAP

[0557] Isosorbide: Isosorbide (CAS: 652-67-5), 99.8%, Polysorb PS A; Roquette Freres (62136 Lestrem, France); abbreviated as ISB

[0558] Lithium hydroxide monohydrate (CAS: 1310-66-3); >99.0%; Sigma-Aldrich

[0559] Terephthalic acid: (CAS: 100-21-0), 99+%, Acros Organics, Gel, Belgium

[0560] Tricyclodecandimethanol: (CAS: 26896-48-0); Isomer mixture; OQ Chemicals, 40789 Monheim, Germany

[0561] Dimer fatty acid: Pripol 1009 (CAS: 68783-41-5); Mn approx. 570 g / mol; hydrogenated, Croda, 41334 Nettetal, Germany

[0562] Sodium (2-ethyl)hexanoate: (CAS: 19766-89-3); 97%; Sigma-Aldrich, Munich, Germany. Dimerdiol: Pripol 2030 (CAS: 147853-32-5); Croda, 41334 Nettetal, Germany. Methyl tert-butyl ether (CAS: 1634-04-4); Azelis Deutschland GmbH, 53757 Sankt Augustin, Germany, abbreviated as MTBE.

[0563] Methyl ethyl ketone (CAS: 78-93-3); Azelis Deutschland GmbH, 53757 Sankt Augustin, Germany, abbreviated as MEK

[0564] Isopropanol (CAS: 67-63-0); Azelis Deutschland GmbH, 53757 Sankt Augustin, Germany Zeolite 4A: Sodium aluminum silicate (CAS: 1318-02-1)

[0565] Polycarbonate based on isosorbide and cyclohexanedimethane 30:70 (CAS: 25037-45-0): producible according to EP2033981 Al; abbreviated as PCI2025PF30041 - Abroad

[0566] - 73 - 2-Butyl-2-ethyl-1,3-propanediol (CAS: 115-84-4); 99.0%; Sigma-Aldrich, Munich, Germany, abbreviated as BEPD

[0567] Toluene (CAS: 108-88-3); 99%; Sigma-Aldrich, Munich, Germany

[0568] 2,2,4-Trimethylpentane or isooctane (CAS: 540-84-1); 99.5%; Sigma-Aldrich, Munich, Germany

[0569] Lipid solution: SmofKabiven central emulsion for infusion; qualitative and quantitative composition: 1000 ml contain: 508 ml amino acid solution with electrolytes, 302 ml glucose solution 42%, 190 ml lipid emulsion. This corresponds to the following total compositions: Alanine 7.1 g, Arginine 6.1 g, Glycine 5.6 g, Histidine 1.5 g, Isoleucine 2.5 g, Leucine 3.8 g, Lysine acetate 3.4 g, Methionine 2.2 g, Phenylalanine 2.6 g, Proline 5.7 g, Serine 3.3 g, Taurine 0.5 g, Threonine 2.2 g, Tryptophan 1.0 g, Tyrosine 0.20 g, Valine 3.1 g, Calcium chloride (as calcium chloride dihydrate) 0.28 g, Sodium glycerophosphate (hydrated) 2.1 g, Magnesium sulfate (as magnesium sulfate heptahydrate) 0.61 g, Potassium chloride 2.3 g, Sodium acetate (as sodium acetate trihydrate) 1.7 g, Zinc sulfate (as zinc sulfate heptahydrate) 0.0066 g, glucose (as glucose monohydrate Ph.Eur.) 127 g, refined soybean oil (Ph.Eur.) 11.4 g, medium-chain triglycerides 11.4 g, refined olive oil 9.5 g, omega-3-rich fish oil 5.7 g.

[0570] Durabio D7340; Copolycarbonate of isosorbide and cyclohexanedimethanol. Phenolic antioxidant: Irganox 1010; CAS 6683-19-8 of BASF SE, Ludwigshafen.

[0571] Phosphorus-containing antioxidant: ADK Stab PEP 36; CAS 80693-00-1 from ADEKA Polymer Additives Europe, Mulhouse, France

[0572] Mold release agent: Loxiol 895; Ethylene glycol distearate; CAS 91031-31-1 / 627-83-8 of Emery Oleochemicals

[0573] Acidic additive: 1,2,3-propanetriol, 1,2,3-tribenzenesulfonate; CAS 81420-25-9

[0574] Analytical methods:

[0575] Solution viscosity:

[0576] The relative solution viscosity (prel; also denoted as eta rel) was determined in dichloromethane at a concentration of 5 g / L at 25 °C using an Ubbelohde viscometer. The determination was carried out according to DIN 51562-3; 1985-05. The flow times of the polyester carbonate being measured through the Ubbelohde viscometer are measured.

[0577] - 74 - Subsequently, the viscosity difference between the polymer solution and its solvent is determined. For this purpose, the Ubbelohde viscometer is first calibrated by measuring the pure solvents dichloromethane, trichloroethylene, and tetrachloroethylene (always at least 3 measurements, at most 9 measurements are taken). The actual calibration is then performed with the solvent dichloromethane. Following this, the polymer sample is weighed out, dissolved in dichloromethane, and the flow time for this solution is then determined three times. The mean of the flow times is corrected using the Hagenbach correction, and the relative solution viscosity is calculated.

[0578] Determination of the glass temperature:

[0579] The glass temperature was determined by differential scanning calorimetry (DSC) according to the standard DIN EN ISO 11357-1:2009-10 and ISO 11357-2:2013-05 at a heating rate of 10 K / min under nitrogen with determination of the glass temperature (Tg) measured as the inflection point in the second heating process.

[0580] Hot water resistance test:

[0581] The polymer samples were boiled under reflux in deionized water for 4 hours and then visually inspected. If they were not completely deformed, they were boiled for another 4 hours under the same conditions and the result visually evaluated.

[0582] Deformation and fracture behavior under impact loading without notch (Charpy impact test):

[0583] Impact bending test with and without a 2mm V-notch in the Charpy test at room temperature, carried out with a self-built drop tester from polymer physics with a 1.86 kg drop mass, dome diameter 20mm, support diameter 62 mm.

[0584] Chemical resistance test (lipid solution, isooctam toluene 1:1):

[0585] At least two flat rods, 80 mm long, 4 mm high, and 10 mm wide, were clamped into a curved template with a radius of 99 cm. This corresponded to a 2% edge fiber strain. The surface of the rods was contaminated by continuous wetting with or complete immersion in the test medium. The time until breakage was measured. The measurement was terminated after 5–14 days.

[0586] Determination of shear rheology: 2025PF30041 - Abroad

[0587] - 75 - The measurement was performed on an ARES-G2 rheometer from TA. The oscillatory frequency sweep test in the range of 0.001 Hz to 10000 Hz was carried out isothermally at 200°C and the complex viscosity was derived from it.

[0588] Determination of scratch resistance:

[0589] To determine scratch resistance, 80x10x4mm flat bars or 60x60x2mm plates were injection molded at 245°C to 260°C. Measurements were taken using an Erichsen test bar 318, equipped with test tip 1 (carbide ball) and a spring with a measuring range of 0-10 N. It was clamped in a frame so that the set force acted on the test tip. The frame and test bar were set to IN and rolled 10 mm over the surface to be tested. If no scratch marks were visually detectable by two testers, the force was increased by 0.5 N and the test was repeated. This process was repeated until a visible scratch mark remained in the polymer. The highest force applied is recorded.

[0590] 'H-NMR spectroscopy:

[0591] The measurements were performed on a Bruker Avance NEO 600 MHz NMR spectrometer. The measurements were carried out in CDCl₃. The samples analyzed contained isosorbide, tricyclodecanedimethanol, and dimerdiol or dimer fatty acid. The molar ratios of these components were evaluated as follows:

[0592] The respective characteristic signals of the monomers were integrated and "normalized" to the number of the respective protons.

[0593] The evaluation of the inventive polymers of Examples 17 (with dimerdiol) and 16 (with dimer fatty acid) is explained here by way of example. Reference is made to Figures 1 and 2.

[0594] For polymers based on a monomer composition of isosorbide, TCD-dimethanol and dimerdiol (here using Pripol 2030; inventive example 17, see Figure 1), the calculation of the molar proportions is carried out as follows:

[0595] The signals between 5.3 and 4.5 ppm were used to determine the isosorbide content. The integral was set to "40" and corresponds to 4 protons of isosorbide.

[0596] The TCD-dimethanol and dimerdiol content was determined from the signals between 4.2 and 3.8. Here, there are 4 isosorbide protons and 2 -CH2- groups of TCD-dimethanol (-O-CH2-) and 2 -CH2- groups of dimerdiol (-O-CH2-). Therefore, this range also contains 4 TCD-dimethanol protons and 4 dimerdiol protons. The relative proportion of TCD-dimethanol could be determined from the range of 2.3 to 1.9 ppm. No dimerdiol protons are present in this range. This range corresponds to 2025PF30041 - Abroad.

[0597] - 76 - approx. 4 protons from TCD-dimethanol. For 1 proton, this resulted in 5.281 / 4 = 1.32. In the signal range between 1.0 and 0.65 ppm, there were 8.3 H from dimerdiol and 1 H from TCD-dimethanol. Thus, the proportion of dimerdiol was 6.527 - 1.32 = 5.207, and therefore 5.207 / 8.3 = 0.627. The relative proportion of TCD-dimethanol to dimerdiol was therefore 1.32 to 0.627. The integral of the range 4.2 to 3.8 ppm was weighted with these proportions. Subtracting the protons from isosorbide, the following adjusted integral was obtained for the protons of dimerdiol and TCD-dimethanol: 47.086 - 40 = 7.086. This integral was weighted with a ratio of 1.32 to 0.627. This resulted in adjusted integrals of 4.80 for TCD-dimethanol and 2.28 for dimerdiol.

[0598] Area Molecule Cleansed Number of Mole Parts Mole % Signal [ppm] Integral Protons

[0599] 5.3 - 4.5 Isosorbide 40 4 10 85.0 4.2 - 3.8 TCD- 4.80 4 1.20 10.2

[0600] Dimethanol

[0601] 4.2 - 3.8 Dimerdiol 2.28 4 0.57 4.8

[0602]

[0603] Z: 11 1.77

[0604] Furthermore, the composition of the inventive example 16 based on a polymer of isosorbide, tricyclodecanedimethanol and dimer fatty acid can also be calculated using the H-NMR spectrum.

[0605] The signals between 5.3 and 4.5 ppm were used to determine the isosorbide content. The integral was set to "40" and corresponds to 4 protons of isosorbide.

[0606] The tricyclodecanadimethanol content was determined from the signals between 4.2 and 3.8 ppm. These signals contain 4 isosorbide protons and 2 -CH2- groups of tricyclodecanadimethanol (-O-CH2-). Therefore, this region also contains 4 tricyclodecanadimethanol protons.

[0607] The dimer fatty acid content was calculated by integrating the signals at 0.95 - 0.6 ppm.

[0608] Here, two CH3 groups of the dimer fatty acid and one proton of tricyclodecanadimethanol are located. Four protons of tricyclodecanadimethanol correspond to 4.931 (the integral at 4.2 to 3.8 ppm is 44.931 - 40 (4 protons of isosorbide) = 4.931). 4.931 / 4 = 1.23, which corresponds to the intensity of one proton of tricyclodecanadimethanol. This signal intensity was subtracted from the integral at 0.95 - 0.6 ppm to obtain the intensity of the CH3 groups of the dimer fatty acid: 4.058 - 1.23 = 2.828. 2025PF30041 - Abroad

[0609] Area Molecule Cleansed Number of Mole Parts Mole % Signal Integral Protons

[0610] [ppm]

[0611] 5.3 - 4.5 Isosorbide 40 4 10 85.4 4.2 - 3.8 TCD- 4.9311 4 1.233 10.5

[0612] Dimethanol

[0613] 0.95 - 0.6 Dimer fatty acid 2.8255 6 0.471 4.0

[0614]

[0615] Z: 11,704

[0616] Production of the starting materials:

[0617] Production of dimer fatty acid diphenyl esters

[0618] 107.32 g (0.501 mol) of diphenyl carbonate and 142.5 g (0.250 mol) of dimer fatty acid were placed in a multi-necked flask with 0.0025 g (100 ppm) of 4-dimethylaminopyridine. The mixture was inerted by four evacuations and venting with nitrogen. The mixture was heated to 160 °C using a metal bath. Carbon dioxide evolved from approximately 140 °C. As soon as the gas flow rate decreased, the temperature was increased to a maximum of 240 °C. Phenol was distilled off during this process. Once gas evolution ceased, a vacuum was applied and the pressure was successively reduced to approximately 1 mbar. The reaction was continued until no further phenol evolved.

[0619] Production of Tetrabutylphosphonium Acetate

[0620] 483.38 g of an aqueous tetrabutylphosphonum hydroxide solution (40% by mass) were placed in an Erlenmeyer flask. Approximately 40 mL (0.7 mol) of pure acetic acid were added dropwise until a pH of approximately 6 was reached. The water was removed by distillation at 80 °C and <0.2 mbar. 200 mL of isopropanol, zeolites (4A) for drying, and 0.5 g of activated carbon for purification were added, and the mixture was allowed to stand in a sealed vessel for at least 12 h. The product was then filtered and concentrated maximally at 80 °C and <0.2 mbar. Upon cooling in a gas-tight vessel, the product crystallized at approximately 40 °C. Color: light brown. 2025PF30041 - Foreign

[0621] - 78 - Preparation of 1,4-cyclohexanedicarboxylic acid diphenyl ester

[0622] 200 g (1.1616 mol) of CHDA, 500 g (2.334 mol) of DPC, and 0.14 g (200 ppm) of DMAP were placed in a 1 L three-necked flask equipped with a distillation bridge. The flask was evacuated four times and inerted with nitrogen to minimize oxygen levels.

[0623] After melting at 180 °C, CO2 was produced. As soon as the flow rate decreased, the temperature was increased to a maximum of 240 °C (phenol distills from approximately 220 °C). After gas evolution was complete (color change), the pressure was reduced to about 50 mbar while the distillation continued. The still was aerated with N2 and the receiver was changed. The pressure was then reduced further. The intermediate fraction was DPC and could also be discarded. The third fraction (<5 mbar, 240 °C) was the main product. Distillation continued until the sump was concentrated to about 50 mL, and the white product was collected after cooling. A slight phenolic odor was noticeable.

[0624] Recrystallization was carried out using a hexane / ethyl acetate mixture (ratio approx. 2:1) with 2-5% of the total mass of activated carbon. The vacuum-filtered product was finely crystalline and bright white.

[0625] Production of terephthalic acid diphenyl esters

[0626] 428.44 g (2.00 mol) of DPC, 162.81 g (0.98 mol) of terephthalic acid, and 0.15 g (250 ppm) of DMAP were placed in a 1 L three-necked flask with a distillation bridge. The flask was evacuated four times and inerted with nitrogen to minimize oxygen levels.

[0627] After heating the suspension to 180 °C, CO2 was produced. As soon as the flow rate decreased, the temperature was increased to a maximum of 260 °C (phenol distills from approximately 220 °C). Once gas evolution was complete (the now clear solution changed color to orange), the pressure was reduced to about 50 mbar while the distillation continued. The unit was aerated with nitrogen and the receiving flask was changed. The pressure was then reduced further. The intermediate fraction was DPC and could also be discarded. As soon as no more distillate was produced, the bottoms were poured off.

[0628] After cooling, the mixture was mechanically ground as finely as possible and refluxed with acetone (the duration depended on the amount of acetone used and the degree of comminution of the crude product). The acetone / diphenyl terephthalate mixture was then cooled to 10 °C and filtered. The intensely yellow mother liquor was discarded, and the pure, finely crystalline product was dried. 2025PF30041 - Abroad

[0629] - 79 - The product had a pearly sheen and a whitish, slightly yellowish color.

[0630] Example 1 (Comparison; PCI)

[0631] Example 2: Polyester carbonate made from 67% isosorbide and 33% CHDA (comparison)

[0632] 51.60 g (0.300 mol) of 1,4-cyclohexanedicarboxylic acid, 89.49 g (0.612 mol) of isosorbide, 192.90 g (0.900 mol) of diphenyl carbonate, 300 ppm DMAP (based on the total mass of all reactants), and 0.365 g (1.15 mmol) of tetrabutylphosphonium acetate were placed in a flask equipped with a short-path separator. The apparatus containing the reactants was purged of oxygen by fourfold evacuation and purging with nitrogen. The mixture was then heated to 160 °C. Once this temperature was reached, carbon dioxide was formed. The temperature was gradually increased to 220 °C over approximately 90 minutes, depending on the observed reactivity. Phenol began to precipitate. The pressure was then gradually reduced to 0.5 mbar over approximately 30 minutes. Stirring continued at this pressure for another 10 minutes.

[0633] A transparent, slightly orange-colored polymer with an eta rel of 1.293 was obtained.

[0634] Example 3: Polyester carbonate from cyclohexanedicarboxylic acid, terephthalic acid, dimer fatty acid and isosorbide (comparison)

[0635] 8.31 g (0.05 mol) of terephthalic acid, 8.60 g (0.05 mol) of CHDA, 4.275 g (0.0075 mol) of dimer fatty acid, and 29.83 g (0.204 mol) of isosorbide were placed in a flask equipped with a short-path separator. Additionally, 13.5 ppm of sodium in the form of sodium 2-ethylhexanoate in MTBE solution (0.5 g / L) and 0.0226 g (200 ppm) of DMAP were added. The contents of the flask were purged of oxygen by fourfold evacuation and purging with nitrogen. The mixture was then melted and heated to 160 °C. Carbon dioxide evolution was observed. Over 60 minutes, the temperature was gradually increased to 225 °C. The pressure was then carefully reduced in several steps to 0.5 mbar over the same period. The temperature was increased to 235 °C. Stirring continued for 10 minutes at 235 °C and 0.5 mbar. A yellow polymer with a relative coefficient (eta rel) of 1.335 was obtained. 2025PF30041 - Abroad

[0636] - 80 - Example 4: Production of a copolycarbonate with dimerdiol without TCD (comparison)

[0637] 64.91 g (0.303 mol) of diphenyl carbonate, 8.1 g (0.015 mol) of Pripol 2030, and 41.65 g (0.285 mol) of isosorbide were placed in a flask equipped with a short-path separator. To this mixture, 0.0001 g of sodium ethylhexanoate in the form of 200 pl of an MTBE solution (0.5 g / L) and 0.00389 g (38.9 pl) of tetrabutylphosphonium acetate in a MEK solution (100 g / L) were added. The mixture was purged of oxygen by four cycles of evacuation and inerting with nitrogen and heated to 160 °C at atmospheric pressure with stirring until melted. Once a homogeneous, low-viscosity liquid was obtained, the temperature was slowly increased to 245 °C with rapid stirring (approx. 500 rpm). Phenol began to distill off at approximately 220 °C. The pressure was then carefully and gradually increased to approximately...

[0638] The pressure was reduced to 0.5 mbar. During this process, phenol was continuously removed. The mixture was stirred at low speed for 10 minutes at approximately 0.5 mbar. A transparent, slightly yellow-tinted polymer with a relative efficiency (eta rel.) of 1.389 was obtained.

[0639] Example 5: Production of a copolycarbonate with dimerdiol without TCD (comparison)

[0640] The experiment was carried out as in Example 4; however, 64.91 g (0.303 mol) of diphenyl carbonate, 10 g (0.0185 mol) of Pripol 2030, and 41.14 g (0.281 mol) of isosorbide were used. A transparent, yellowish polymer with a relative efficiency (eta rel) of 1.329 was obtained.

[0641] Example 6: Production of a copolycarbonate with dimerdiol without TCD (comparison)

[0642] The experiment was carried out as in Example 4; however, 64.91 g (0.303 mol) of diphenyl carbonate, 11.79 g (0.022 mol) of Pripol 2030, and 40.65 g (0.278 mol) of isosorbide were used. A transparent, yellowish polymer with a relative efficiency (eta rel) of 1.382 was obtained.

[0643] Example 7: Polycarbonate made from isosorbide and BEPD (comparison)

[0644] 29.83 g (0.204 mol) of isosorbide, 64.3 g (0.3 mol) of diphenyl carbonate, and 20 ppm lithium in the form of 75 pL LiOH solution (100 g LiOH / L) were placed in a flask equipped with a short-path separator. The flask contents were purged of oxygen by fourfold evacuation and venting with nitrogen. The mixture was heated to 180 °C. After 15 minutes, 16.35 g (0.102 mol) of 2-butyl-2-ethyl-1,3-propanediol were added. The temperature was gradually increased to 225 °C over 30 minutes. Phenol began to separate. The pressure was carefully reduced to 0.5 mbar over 45 minutes. The temperature was increased to 235 °C. The mixture was stirred for another 10 minutes at this temperature and pressure. A transparent polymer with a relative eta of 1000 was obtained. from 1,202.2025PF30041 - Abroad

[0645] - 81 - Example 8: Polyester carbonate with a low CHDA content (comparison)

[0646] 4.42 g (0.0225 mol) of tricyclodecanedimethanol, 2.673 g (0.0083 mol) of 1,4-cyclohexanedicarboxylic acid diphenyl ester, and 4.87 g (0.0068 mol) of diphenyl fatty acid diphenyl ester were placed in a flask equipped with a short-path separator and dropping funnel. Furthermore, 0.0015 g (15 pl) of lithium hydroxide in the form of an aqueous solution (100 g / L) was added. The mixture was purged of oxygen by four cycles of evacuation and interting with nitrogen, melted, and heated to 160 °C at atmospheric pressure with stirring. Depending on the observed reactivity, the temperature was gradually increased to a maximum of 210 °C. The pressure was then reduced to approximately 50 mbar and held for 15 minutes to remove phenol. The mixture was then aerated with nitrogen to ambient pressure, and 16.66 g (0.1140 mol) of isosorbide and 25.71 g (0.1200 mol) of diphenyl carbonate were added to the reaction mixture at 225 °C with rapid stirring. After complete addition, phenol distilled off.The temperature was increased to 235 °C and the pressure carefully and gradually reduced to <1 mbar, during which time phenol was continuously removed. The mixture was stirred for another 10 minutes at low speed at approximately 0.5 mbar. A transparent, yellowish polymer with a solution viscosity of 1.27 was obtained.

[0647] Example 9 (Comparison; polyester carbonate with CHDA and TCD)

[0648] 7.86 g (0.04 mol) of tricyclodecanedimethanol and 11.66 g (0.036 mol) of 1,4-cyclohexanedicarboxylic acid diphenyl ester were placed in a flask equipped with a short-path separator and dropping funnel. Furthermore, 0.0015 g (15 pl) of lithium hydroxide in the form of an aqueous solution (100 g / L) was added. The mixture was purged of oxygen by four cycles of evacuation and inerting with nitrogen, melted, and heated to 160 °C at atmospheric pressure with stirring. Depending on the observed reactivity, the temperature was gradually increased to a maximum of 210 °C. The pressure was then reduced to approximately 50 mbar and held for 15 minutes to remove phenol. The mixture was then aerated with nitrogen to ambient pressure, and 16.66 g (0.1140 mol) of isosorbide and 25.71 g (0.1200 mol) of diphenyl carbonate were added to the reaction mixture at 225 °C with rapid stirring. After complete addition, phenol distilled off.The temperature was increased to 235 °C and the pressure carefully and gradually reduced to <1 mbar, during which time phenol was continuously removed. At approximately 0.5 mbar, the mixture was stirred for another 10 minutes at low speed. A transparent, yellowish polymer with a solution viscosity of 1.27.2025PF30041 - Abroad was obtained.

[0649] - 82 - Example 10 (Comparison)

[0650] 64.91 g (0.303 mol) of diphenyl carbonate, 17.67 g (0.09 mol) of tricyclodecanedimethanol, and 30.69 g (0.210 mol) of isosorbide were placed in a flask equipped with a short-path separator. To this mixture, 0.0001 g of sodium ethylhexanoate in the form of 200 pl of an MTBE solution (0.5 g / L) and 0.00389 g (38.9 pl) of tetrabutylphosphonium acetate in a MEK solution (100 g / L) were added. The mixture was purged of oxygen by four cycles of evacuation and inerting with nitrogen and heated to 160 °C at atmospheric pressure with stirring until melted. Once a homogeneous, low-viscosity liquid was obtained, the temperature was slowly increased to 245 °C with rapid stirring (approximately 500 rpm). Phenol began to distill off at approximately 220 °C. The pressure was then carefully and gradually increased to approximately...

[0651] The pressure was reduced to 0.5 mbar and simultaneously the temperature increased to up to 255 °C. Phenol was continuously removed during this process. The mixture was stirred at low speed for another 10 minutes at approximately 0.5 mbar. A slightly cloudy, yellow-colored polymer with a relative efficiency (eta rel.) of 1.294 was obtained.

[0652] Example 11 (Comparison)

[0653] 70.32 g (0.3283 mol) of diphenyl carbonate, 5.90 g (0.03 mol) of tricyclodecanedimethanol, 8.10 g (0.04 mol) of 1,12-dodecanediol, and 37.27 g (0.255 mol) of isosorbide were placed in a flask equipped with a short-path separator. To this mixture, 0.0001 g of sodium ethylhexanoate in the form of 200 pl of an MTBE solution (0.5 g / L) and 0.00389 g (38.9 pl) of tetrabutylphosphonium acetate in a MEK solution (100 g / L) were added. The mixture was purged of oxygen by four cycles of evacuation and inerting with nitrogen and heated to 160 °C at atmospheric pressure with stirring until melted. Once a homogeneous, low-viscosity liquid was obtained, the temperature was slowly increased to 245 °C while stirring rapidly (approx. 500 rpm). Phenol began to distill off at approximately 220 °C. The pressure was then carefully and gradually reduced to approximately 0.5 mbar, while the temperature was simultaneously increased to 255 °C. During this process, phenol was continuously removed. At approximately...The mixture was stirred at low speed for 10 minutes at 0.5 mbar. A transparent, yellow-colored polymer with a relative efficiency (eta rel.) of 1.191 was obtained.

[0654] Example 12 (Comparison)

[0655] 73.65 g (0.344 mol) of diphenyl carbonate, 5.90 g (0.03 mol) of tricyclodecanedimethanol, 8.10 g (0.0554 mol) of octanediol, and 37.27 g (0.255 mol) of isosorbide were placed in a flask equipped with a short-path separator. To this mixture, 0.0001 g of sodium ethylhexanoate in the form of 200 pl of an MTBE solution (0.5 g / L) and 0.00389 g of 2025PF30041 - foreign country were added.

[0656] - 83 - (38.9 pl) Tetrabutylphosphonium acetate was added to a MEK solution (100 g / L). The mixture was deoxygenated by fourfold evacuation and inerting with nitrogen and heated to 160 °C at atmospheric pressure with stirring until melted. Once a homogeneous, low-viscosity liquid was obtained, the temperature was slowly increased to 245 °C with rapid stirring (approx. 500 rpm). Phenol began to distill off at approximately 220 °C. The pressure was then carefully and gradually reduced to approximately 0.5 mbar, while the temperature was simultaneously increased to 255 °C. Phenol was continuously removed during this process. Stirring continued at low speed for 10 minutes at approximately 0.5 mbar. A cloudy, brown-colored polymer with a relative efficiency (eta rel.) of 1.076 was obtained.

[0657] Example 13 (Comparison)

[0658] 70.32 g (0.3283 mol) of diphenyl carbonate, 5.90 g (0.03 mol) of tricyclodecanedimethanol, 8.10 g (0.040 mol) of sebacic acid, and 37.1 g (0.255 mol) of isosorbide were placed in a flask equipped with a short-path separator. To this mixture, 0.0001 g of sodium ethylhexanoate in the form of 200 pl of an MTBE solution (0.5 g / L), 0.00389 g (38.9 pl) of tetrabutylphosphonium acetate in a MEK solution (100 g / L), and 0.0243 g (200 ppm) of DMAP were added. The mixture was purged of oxygen by four cycles of evacuation and inerting with nitrogen and heated to 160 °C at atmospheric pressure with stirring until melted. Once a homogeneous, low-viscosity liquid was obtained, the temperature was slowly increased to 245 °C while stirring rapidly (approx. 500 rpm). Carbon dioxide evolution was observed, and distillation of phenol began at approximately 220 °C. After gas evolution ceased, the pressure was carefully and gradually reduced to approximately...The pressure was reduced to 0.5 mbar and simultaneously the temperature increased to up to 255 °C. During this process, phenol was continuously removed. The mixture was stirred at low speed for another 10 minutes at approximately 0.5 mbar. A slightly cloudy, light brown polymer with a relative efficiency (eta rel.) of 1.338 was obtained.

[0659] Example 14 (Comparison)

[0660] 64.91 g (0.303 mol) of diphenyl carbonate, 5.90 g (0.03 mol) of tricyclodecanedimethanol, 26.5 g (0.045 mol) of Pripol 2030, and 32.88 g (0.225 mol) of isosorbide were placed in a flask equipped with a short-path separator. To this mixture, 0.0001 g of sodium ethylhexanoate in the form of 200 pl of an MTBE solution (0.5 g / L) and 0.00389 g (38.9 pl) of tetrabutylphosphonium acetate in an MEK solution (100 g / L) were added. The mixture was purged of oxygen by four cycles of evacuation and inerting with nitrogen and heated to 160 °C at atmospheric pressure with stirring until melted. Once a homogeneous, low-viscosity liquid was obtained, the temperature was rapidly reduced.

[0661] - 84 - Stirring (approx. 500 rpm) was slowly increased to 245 °C. Phenol distilled off starting at approx. 220 °C. The pressure was then carefully and gradually reduced to approx. 0.5 mbar, while the temperature was simultaneously increased to 255 °C. Phenol was continuously removed during this process. Stirring continued at low speed for 10 minutes at approx. 0.5 mbar. A transparent, pale yellow polymer with a relative efficiency (eta rel.) of 1.423 was obtained.

[0662] Example 15 (Comparison)

[0663] 64.91 g (0.303 mol) of diphenyl carbonate, 26.50 g (0.135 mol) of tricyclodecanedimethanol, 8.1 g (0.015 mol) of Pripol 2030, and 21.92 g (0.150 mol) of isosorbide were placed in a flask equipped with a short-path separator. To this mixture, 0.0001 g of sodium ethylhexanoate in the form of 200 pl of an MTBE solution (0.5 g / L) and 0.00389 g (38.9 pl) of tetrabutylphosphonium acetate in a MEK solution (100 g / L) were added. The mixture was purged of oxygen by four evacuations and interstitial injections with nitrogen and heated to 160 °C at atmospheric pressure with stirring until melted. Once a homogeneous, low-viscosity liquid was obtained, the temperature was slowly increased to 245 °C while stirring rapidly (approx. 500 rpm). Phenol began to distill off at approximately 220 °C. The pressure was then carefully and gradually reduced to approximately 0.5 mbar, while the temperature was simultaneously increased to 255 °C. During this process, phenol was continuously removed. At approximately...The mixture was stirred at low speed for 10 minutes at 0.5 mbar. A slightly cloudy, light yellow polymer with a relative efficiency (eta rel.) of 1.339 was obtained.

[0664] Example 16: Production of a polyester carbonate containing dimer fatty acid (reference)

[0665] 29.22 g (0.0405 mol) of diphenyl dimer fatty acid ester, 17.7 g (0.09 mol) of tricyclodecanedimethanol, and 0.0003 g (943.5 ppb) of sodium 2-ethylhexanoate in solution (5 g / L in MTBE), as well as 0.0115 g (36 ppm) of tetrabutylphosphonium acetate in solution (100 g / L in MEK), were placed in a flask equipped with a short-path separator and dropping funnel. The mixture was purified of oxygen by fourfold evacuation and interting with nitrogen, melted, and heated to 160 °C at atmospheric pressure with stirring. Depending on the observed reactivity, the temperature was gradually increased to a maximum of...

[0666] The temperature was increased to 210 °C. The pressure was then reduced to approximately 50 mbar and held for 15 minutes to remove phenol. Afterward, the mixture was purged with nitrogen to ambient pressure, and 177.21 g (0.8272 mol) of diphenyl carbonate and 112.45 g (0.7695 mol) of isosorbide were added to the reaction mixture at 225 °C with rapid stirring. After complete addition, the phenol distilled off. The temperature was increased to 235 °C, and the pressure was carefully and gradually reduced to <1 mbar, continuously removing phenol. 2025PF30041 - Abroad

[0667] - 85 - At approximately 0.5 mbar, the mixture was stirred for another 10 minutes at low speed. A light yellow polymer with a relative efficiency (eta rel) of 1.240 was obtained.

[0668] Example 17: Production of a copolycarbonate with dimerdiol (reference)

[0669] 194.73 g (0.909 mol) of diphenyl carbonate, 24.3 g (0.045 mol) of Pripol 2030, 17.7 g (0.090 mol) of tricyclodecanedimethanol, and 111.8 g (0.765 mol) of isosorbide were placed in a flask equipped with a short-path separator. To this mixture, 0.001 g of sodium ethylhexanoate in the form of 600 µl of an MTBE solution (0.5 g / L) and 116.5 pL g of tetrabutylphosphonium acetate in a MEK solution (100 g / L) were added. The mixture was purged of oxygen by four cycles of evacuation and interting with nitrogen, melted, and heated to 160 °C at atmospheric pressure with stirring until completely melted. Once a homogeneous, low-viscosity liquid was obtained, the temperature was slowly increased to 245 °C while stirring rapidly (approx. 500 rpm). Phenol began to distill off at approximately 220 °C. The pressure was then carefully and gradually reduced to approximately 0.5 mbar. During this process, phenol was continuously removed. Stirring continued at low speed for another 10 minutes at approximately 0.5 mbar.A light-colored, transparent polymer with a relative efficiency of 1.356 was obtained.

[0670] Example 18: Production of a copolycarbonate with dimerdiol (reference)

[0671] The experiment was carried out as in Example 17; however, 194.73 g (0.909 mol) of diphenyl carbonate, 30.0 g (0.055 mol) of Pripol 2030, 14.75 g (0.075 mol) of tricyclodecanedimethanol, and 112.45 g (0.7695 mol) of isosorbide were used. A light yellow polymer with a relative efficiency (eta rel) of 1.320 was obtained.

[0672] Example 19: Production of a copolycarbonate with dimerdiol (reference)

[0673] The experiment was carried out as in Example 17; however, 194.73 g (0.909 mol) of diphenyl carbonate, 27.0 g (0.05 mol) of Pripol 2030, 17.7 g (0.09 mol) of tricyclodecanedimethanol, and 111.07 g (0.760 mol) of isosorbide were used. A pale yellow polymer with a relative efficiency (eta rel) of 1.325 was obtained.

[0674] Example 20: Production of a copolycarbonate with dimerdiol (reference)

[0675] The experiment was carried out as in Example 17; however, 32.46 g (0.1515 mol) of diphenyl carbonate, 4.05 g (0.0075 mol) of Pripol 2030, 4.43 g (0.0335 mol) of tricyclodecanedimethanol, and 17.54 g (0.120 mol) of isosorbide were used. A light yellow polymer with a relative efficiency (eta rel) of 1.352 was obtained. 2025PF30041 - Abroad

[0676] - 86 - Example 21: Production of a copolycarbonate with dimerdiol (reference)

[0677] The experiment was carried out as in Example 17; however, 64.91 g (0.303 mol) of diphenyl carbonate, 8.10 g (0.015 mol) of Pripol 2030, 5.02 g (0.0255 mol) of tricyclodecanedimethanol, and 37.92 g (0.2595 mol) of isosorbide were used. A pale yellow polymer with a relative efficiency (eta rel) of 1.331 was obtained.

[0678] Example 22: Production of a copolyester carbonate containing dimer fatty acid and terephthalic acid (reference)

[0679] 64.23 g (0.300 mol) of diphenyl carbonate, 4.95 g (0.0253 mol) of tricyclodecanedimethanol, 11.21 g (0.0625 mol) of terephthalic acid, 4.28 g (0.0075 mol) of dimer fatty acid, and 29.52 g (0.202 mol) of isosorbide were placed in a flask equipped with a short-path separator. To this mixture, 0.00571 g of tetrabutylphosphonium acetate and 0.0114 g of DMAP were added. The mixture was purged of oxygen by four cycles of evacuation and inerting with nitrogen and heated to 160 °C at atmospheric pressure with stirring until melted. Once a homogeneous, low-viscosity liquid was obtained, the temperature was slowly increased to 245 °C with rapid stirring (approximately 500 rpm). Carbon dioxide evolution was observed, and distillation of phenol began at approximately 220 °C. Once gas evolution ceased, the pressure was carefully and gradually reduced to approximately 0.5 mbar, while the temperature was simultaneously increased to 255 °C. During this process, phenol was continuously removed. At approximately...The mixture was stirred at low speed for 10 minutes at 0.5 mbar. A transparent, reddish polymer with a relative efficiency of 1.206.2025PF30041 was obtained.

[0680] - 87 - Table 1: Hot water resistance

[0681] Bs Bs e.g. Polymer structure appearance after Tg P hot water test

[0682] No.

[0683] 1. Comparison example: PC made from 70% ISB and 30% turbidity, some bubbles, 122°C PCI % CHDM

[0684] 2. Comparison examples: PEC standard opaque, blister-like, brittle 150 °C CHDA / ISB (previously transparent)

[0685] 3. Comparative examples: PEC made from ISB / CHDA, TA, opaque (previously 134 °C DFA transparent)

[0686] 4. Comparative example: ISB + Dimerdiol without clear, transparent 138 °C TCD; 12.5 wt%

[0687] Dimerdiol

[0688] 5. Comparative example: ISB + Dimerdiol without clear, transparent 132 °C TCD; 17 wt%

[0689] Dimerdiol

[0690] 6. Comparative example: ISB + Dimerdiol without clear, transparent 127 °C TCD; 20 wt%

[0691] Dimerdiol

[0692] 7. Comparative example: P(l67BEPD33) Cloudy, swollen, brittle, 131 °C. 8. Comparative example: PEC with low opacity, vesicular, 132 °C on CHDA; surface P(I75C5,5DFA4,5TCD15)

[0693] 9. Comparative example: P(l50.5C23TCD25.5) Opaque; surface deformed at 127 °C

[0694] 10 comparison examples: ISB + TCD without clear, transparent 135 °C

[0695] Dimerdiol

[0696]

[0697] 2025PF30041 Abroad

[0698] - 88 - 11 Comparative example: Pripol replaced by Dodecanediol Opaque, bubbly 99 °C;

[0699] 12. Comparative example: Pripol replaced by clear, bubbly octanediol <100°C; C

[0700] 13. Comparative example: Approach with sebacic acid, opaque, bubbly, 114 °C instead of Pripol

[0701] 14. Comparative example: Too high a Pripol content; opaque, whitish, light 91 °CI75 TCDioPi5 Surface Deformation

[0702] n

[0703] 15. Comparative example: Too high a TCD content; opaque, whitish, distinct surface deformation at 82 °C I50TCD45P5

[0704] n

[0705] 16 Reference example P(I85,5DFA4,5TCD1O) Clear, transparent 111 °C

[0706] 17 reference examples P(I85Pripol20305TCDio) Clear, transparent 123 °C

[0707] 18 Reference examples P(I 85 ,5Pripol Clear, transparent 117 °C 20306,2TCD8,3)

[0708] 19 Reference example P(I84,5Pripol Clear, transparent 117 °C 2O3O5,5TCDIO)

[0709] 20 Reference examples P(I 80 Pripol20305TCDi5) Clear transparent 113 °C

[0710] 21 Reference example P(I 87 Pripol20304.5TCD8.5) Clear transparent 124 °C

[0711] 22 Reference example P(l67DFA2,5TCD8,45TA22,5 Clear transparent 132

[0712] )

[0713]

[0714] 2025PF30041 Abroad

[0715] - 89 - Table 2: Further resistance tests

[0716] Example: Rapeseed oil lipid solution isooctane / toluene No. (1:1)

[0717] 1 PCI; Comparison Fraction; Fraction; <10 s Fraction; <10 s 9 min

[0718] 10 Comparison example (P(l7oBD02TCD2s) Fracture; Fracture; Id >7d; Edge cracks 4h 42min

[0719] 17 reference examples >5d >5 d >7 d

[0720] 16 reference examples >5d >7d >7d

[0721]

[0722] Table 3: Shear rheology

[0723] Example: Complex viscosity [Pas] Complex viscosity [Pas] at 0.01 Hz 1 Hz

[0724] 4 Comparison l,2xl0 6 l,0xl0 5

[0725] 5 Comparison 5.0xl0 5 6.6xl0 4

[0726] 6 Comparison 7.6xl0 5 7,lxl0 4

[0727] 16 Reference examples 3.4xl0 4 l,6xl0 4

[0728] 18 Reference example 5,lxl0 4l,9xl0 4

[0729] 19 Reference example 5,lxl0 4 2.4x10 4

[0730]

[0731] It is recognized that the copoly(ester) carbonates used in accordance with regulations exhibit high stability against hot water. Surprisingly, polymers made from commonly used diols such as cyclohexanedimethane and isosorbide (Example 1) – as described, for example, in EP 2033981 – are not very stable against hot water exposure. Other diols, such as the combination of sterically hindered diols like isosorbide and 2-butyl-2-ethyl-1,3-propanediol, also do not exhibit good stability (Example 7). This is surprising since these sterically hindered diols, such as BEPD or neopentyl glycol, normally improve hydrolysis stability. Example 2 shows that polyester carbonates made from 1,4-cyclohexanedicarboxylic acid and 2025PF30041 - Abroad

[0732] - 90 - Isosorbide also did not show good stability in the hot water test. This was surprising, since polyesters, e.g., made from cyclohexanediethanol and 1,4-cyclohexanedicarboxylic acid, exhibit high stability against aqueous media.

[0733] Example 11 shows that the combination of isosorbide and long-chain diols – such as dodecanediol (see EP2840102) in this case – did not necessarily lead to a better result. This polymer also exhibited significant weaknesses in the hot water test. These polymers can also be disadvantageous in other respects; for example, they often have low glass transition temperatures.

[0734] It is known that aromatic polyesters are often stable against hot water. For example, polyesters such as polyethylene terephthalate and corresponding derivatives are stable against hot water. However, the incorporation of aromatic diacids such as terephthalic acid or isophthalic acid into a polycarbonate or polyester carbonate otherwise composed of aliphatic building blocks—as shown in Example 3—surprisingly does not lead to stable products. The incorporation of dimer fatty acids into such structures also does not help. One would have expected that the nonpolar or hydrophobic properties of the aromatic acids or the dimer fatty acid would improve stability against water. Surprisingly, this also applies, in part, to polymers containing TCD alcohol. For example, a polymer consisting of isosorbide, cyclohexanedicarboxylic acid, dimer fatty acid, and TCD dimethanol is surprisingly unstable (Example 8). This can be attributed to the presence of the cyclohexanedicarboxylic acid.

[0735] Surprisingly, polymers consisting essentially of isosorbide and long-chain nonpolar fatty acids such as sebacic acid are also not stable against hot water (Example 13).

[0736] The combination of dimerdiol or dimer fatty acid and isosorbide exhibits high resistance to aqueous media. Surprisingly, however, these polymers show a high melt viscosity (Examples 4 to 6). Rheological investigations confirm that the viscosity is significantly higher compared to the polymers of the invention. The high melt viscosity is a crucial disadvantage because it makes processing these materials considerably more difficult. A significant increase in process temperatures to improve flowability is not possible with aliphatic materials, as they are not as stable as, for example, aromatic polycarbonates and therefore tend to decompose and lose molecular weight at higher process temperatures. Surprisingly, the polymers of the invention exhibit better surface hardness than polycarbonates based on bisphenol A and also than polymers based on ISB2025PF30041 - Abroad.

[0737] - 91 -and dimerdiol (see Table 4 below). Polymers with a high proportion of TCD alcohol do not exhibit good properties in the hot water test (Example 15). It was therefore very surprising that only the copoly(ester)carbonates used according to the invention with the inventive proportions of units (A), (B) and (C) exhibit both high hot water stability and good stability against solvents such as fuel mixtures (isooctane-toluene mixture) and at the same time show high surface hardness with sufficiently good mechanical properties.

[0738] It can also be seen that the polymers according to the invention have glass transition temperatures of more than 110 °C.

[0739] Table 4: Scratch resistance

[0740] Example composition scratch resistance Tg Eta rel.

[0741] (N) (°C)

[0742] 4 (Comparison) P(I95Pripol20305) 4.5-5 137 1.389

[0743] 5 (comparison) P(l94Pripol2030e) 3.5 132 1.329

[0744] 6 (Comparison) P(l92,7Pripol20307,3) 2 - 2,5 135 1,382

[0745] 17 (reference example) P(I85Pripol20305TCDio) 9-10 123 1.356

[0746] 20 (reference example) P(I 80 Pripol20305TCDi5) 7.5-8 113 1.352

[0747]

[0748] The results in Table 4 show that with increasing Pripol content and in the absence of TCD-dimethanol, the scratch resistance decreases (although the Tg and molecular weight do not vary significantly between the tests). In contrast, the copolymers according to the invention with lower Tg but with TCD-dimethanol as a comonomer exhibit better scratch resistance. 2025PF30041 Abroad

[0749] - 92 - Table 5: Charpy impact test

[0750] Example Charpy test; unnotched

[0751] 18 10 x not broken

[0752] 16 10 x not broken

[0753] 17 10 x not broken

[0754]

[0755] Table 6: 'H-NMR spectroscopy'

[0756] ISB (mol%) TCD-DM (mol%) Dimer fatty acid / dimer diol (mol%)

[0757] Reference example 85.4 10.5 4.0

[0758] 16

[0759] Reference example 85.0 10.2 4.8

[0760] 17

[0761] Reference example 85.3 8.9 5.8

[0762] 18

[0763] Reference example 84.6 10.1 5.3

[0764] 19

[0765] Reference example 86.8 8.4 4.8

[0766] 21

[0767] Reference example 80.1 14.8 5.1

[0768] 20

[0769]

[0770] As can be seen from Table 6, the monomers used are almost completely incorporated into the copoly(ester) carbonate. Thus, the molar ratios of the monomers used remain almost entirely intact in the copoly(ester) carbonate. This means that the ratio and quantity of the structural units present in the resulting polymer can be controlled by adjusting the ratio and quantity of the starting materials. 2025PF30041 - International

[0771] - 93 - Example 22 (according to invention)

[0772] A copolyester carbonate consisting of isosorbide, TCD-dimethanol, and dimeric acid (85 / 10 / 5 mol%) was melted on an extruder (ZSK 27 at 110 rpm and 240 °C) and mixed with additives in the final housing section via a side extruder (a single-shaft extruder with a 25 mm shaft diameter and a length-to-diameter ratio of 18; manufactured by ESDE Maschinentechnik GmbH, type ESE 1-25-18). Granules were obtained, and the solution viscosity (ηrel) was determined.

[0773] Durabio D7340 was used as the carrier for the additives. A phenolic antioxidant, phosphorus stabilizer, demolding agent, and acid-containing additive (see material list above) were added via the masterbatch, resulting in the quantities listed in the table for the total composition.

[0774] Component Amount in Polymer (wt% or ppm) Durabio D7340 4.00%

[0775] Irganox 1010 (phenolic 0.037%)

[0776] Antioxidants)

[0777] ADK rod PEP 36 (phosphorus containing 37 ppm

[0778] Antioxidants

[0779] Loxiol 895 0.18%

[0780] Sulfonic acid esters (acidic 3.7 ppm)

[0781] Additive)

[0782]

[0783] Example 23: Comparison example without additives

[0784] A copolyester carbonate consisting of isosorbide, TCD-dimethanol, and dimeric acid (85 / 10 / 5 mol%) was melted and extruded on an extruder (ZSK 27 at 110 rpm and 240 °C) as in Example 22. Unlike Example 22, no additives were added. Granules were obtained, and the solution viscosity (ηrel) was determined.

[0785] Injection molding:

[0786] The compositions of Example 22 and Example 23 were dried at 80 °C in a vacuum drying oven for 4 hours.

[0787] Standard bars with dimensions 80x10x3 mm were produced using a Boy XS injection molding machine at a cylinder temperature of 250 °C, a mold temperature of 70 °C, and an injection pressure of 1720 bar. The solution viscosity (eta rel) was determined. 2025PF30041 Abroad

[0788] - 94 -

[0789] Viscosity:

[0790] E.g. Eta rel Granules Eta rel Rod Delta

[0791] Example 22 (Exp.) 1.283 1.272 0.011

[0792] Example 23 (cf.) 1.290 1.255 0.035

[0793]

[0794] The solution viscosities show that the additive-treated polymer degrades significantly less under thermomechanical stress (injection molding process) compared to the non-additive-treated polymer.

Claims

2025PF30041 - Abroad Patent claims:

1. Thermoplastic composition comprising (I) a copoly(ester) carbonate comprising the units (A), (B), (C), optionally (D) and optionally units different from (A), (B), (C) and (D), with O _ rr _ / nui \ _ _ / r*u \- KZ r ' \'-' n 2 / s (B), where each r and each s independently represents a number between 0 and 4, and each R 1 independently of each other stands for a structure of the formulas (RIA), (RIB), (R1C) or (R1D). (RIO, (R1D), where the with The marked positions in formulas (RIA) to (R1D) are the positions where the (CTOf group or (CH2)s group shown in formula (B) is located, and 2025PF30041 abroad - 96 - O #— (O) t — R 2 — (O) t — (C), where both t are independent of R 2 simultaneously either 0 or simultaneously 1, and each R 2 independently of each other stands for an aliphatic group with 16 to 44 carbon atoms, which may contain one or more double bonds, ■O . (D), wherein at least partially direct links exist between the units (A), (B), (C), optionally (D) and, where appropriate, units different from (A), (B), (C) and (D), wherein, if a direct link exists between at least two of the units selected from the group consisting of (A), (B), (C) and, where appropriate, (D), the position of the units (A), (B), (C), (D) marked with is then linked to the units marked with the marked position of these units is linked, with the exception that if t in formula (C) is 0, there is no direct link between two units (C), if t in formula (C) is 0, there is no direct link between unit (C) and unit (D) and no direct connection exists between two units (D), wherein the copoly(ester)carbonate contains 4 to 25 mol% of unit (B), 2 to 14 mol% of unit (C), 0 to 5 mol% of unit (D) and at least 55 mol% of unit (A), wherein the mol% values ​​refer to the total amount of substance of units (A), (B), (C), where applicable (D) and where applicable units other than (A), (B), (C) and (D) and (II) at least one additive selected from the group consisting of (Ila) a UV absorber selected from the group consisting of benzotriazole compounds, benzophenone compounds, triazine compounds, benzoate compounds, phenyl salicylate compounds, cyanoacrylate compounds, malonic acid ester compounds and oxalanilide compounds, (Hb) a sterically hindered amine light stabilizer, (IIc) a bluing agent, (Ild) an antioxidant, 2025PF30041 - Abroad - 97 - (all) a lubricant and release agent selected from the group consisting of fatty acids with 10 to 30 carbon atoms, their fatty acid esters of mono- or polyhydric alcohols, natural animal waxes, natural vegetable waxes, natural petroleum-based waxes, montan waxes, olefin waxes, silicone oils and organopolysiloxanes, (llf) an acid-containing additive, (llg) an OH and acid group scavenger, (llh) of an alkaline compound, (lli) a reducing agent (llj) an antistatic agent selected from the group consisting of polyetheresteramides, glycerol monostearate, ammonium salts of dodecylbenzenesulfonic acid, phosphonium salts of dodecylbenzenesulfonic acid, quaternary ammonium salts of a perfluoroalkylsulfonic acid, maleic anhydride monoglyceride and maleic anhydride diglyceride, (llk) a colorant selected from the group of inorganic pigments, which include carbon black, titanium oxide, zinc white, iron oxide red, chromium oxide, iron black, titanium yellow, zinc-iron brown, copper-chromium black, copper-iron black and oxide-based pigments, organic pigments and organic dyes, which include phthalocyanine dyes and pigments; condensed polycycles such as azo, thioindigo, perinone, perylene, quinacridone, dioxazine, isoindolinone and quinophthalone dyes and pigments, anthraquinone, perinone, perylene, methine, quinoline, heterocycle and methyl-based dyes and pigments, (13) an inorganic filler, (llm) a flame retardant selected from the group consisting of phosphorus compound-based, halogen compound-based, metal sulfonate-based and silicon compound-based flame retardants, (lln) a polymeric blend partner selected from the group consisting of poly(lactic acid), poly(cyclohexanedimethanol-cyclohexanedicarboxylate), poly(propylene terephthalate), polycarbonates, polyamide 46, polyamide 12, semiaromatic polyamides, rubber-modified graft polymers, vinyl(co)polymers selected from the group (co)polymers of B.1 50 to 99 wt.%, preferably 65 to 85 wt.%, particularly preferably 70 to 80 wt.% based on the (co)polymer of at least one monomer selected from the group of vinyl aromatics, keme-substituted vinyl aromatics and (meth)acrylic acid (C1-C8) alkyl esters and 2025PF30041 - Abroad B.2 1 to 50 wt.%, preferably 15 to 35 wt.%, particularly preferably 20 to 30 wt.% based on the (co)polymer of at least one monomer selected from the group consisting of vinyl cyanides, (meth)acrylic acid (Cl-C8) alkyl esters, unsaturated carboxylic acids and derivatives of unsaturated carboxylic acids, Polyolefins selected from the group consisting of polyethylene, ethylene copolymers, polypropylene and 4-methylpentene-l resins, polyacetals, poly(amidoimides), poly(ethersulfones), polyimides, poly(phenylene oxide), poly(phenylene sulfide), poly(phenylsulfone), polyetheretherketone, liquid crystalline polyesters, poly(vinyl chloride) and fluorinated resins.

2. Thermoplastic composition according to claim 1, characterized in that (Ilb) the sterically hindered amine light stabilizer comprises one or more structural units according to formula (30), Y (30) where in formula (30) Y fur H, R 2or OR 2 stands and R 2 stands for branched or unbranched Ci-Cis-alkyl, C2-C2o-alkenyl, Ce-Cn-aryl or -CO-Ci-Ci8-alkyl.

3. Thermoplastic composition according to one of claims 1 or 2, characterized in that the (IIc) bluing agent is an anthraquinone dye.

4. Thermoplastic composition according to one of claims 1 to 3, characterized in that the (Ild) antioxidant is selected from sterically hindered phenols, a phosphorus-containing antioxidant and a sulfur-containing antioxidant.

5. Thermoplastic composition according to one of claims 1 to 4, characterized in that the (Ilg) OH and acid group scavenger is a compound containing an epoxy group or a carbodiimide group.

6. Thermoplastic composition according to one of claims 1 to 5, characterized in that the alkaline compound is an alkali metal salt.

7. Thermoplastic composition according to any one of claims 1 to 6, characterized in that the reducing agent is sodium borohydride or lithium borohydride. 2025PF30041 - Abroad - 99 - 8. Thermoplastic composition according to one of claims 1 to 7, characterized in that the (III) inorganic filler is selected from the group consisting of glass fibers, ground glass fibers, glass flakes, glass beads, carbon fiber, silica, aluminum oxide, titanium oxide, calcium sulfate powder, gypsum, gypsum whiskers, barium sulfate, talc, mica, calcium silicate such as wollastonite, carbon black, graphite, iron powder, copper powder, molybdenum disulfide, silicon carbide, silicon carbide fiber, silicon nitride, silicon nitride fiber, brass fiber, stainless steel fiber, potassium titanate fiber and whiskers.

9. Thermoplastic composition according to any one of claims 1 to 8, characterized in that the (Iln) polymeric blend partner is a rubber-modified graft polymer which B.1a 5 to 95 wt.%, preferably 20 to 92 wt.%, in particular 30 to 91 wt.%, based on the graft polymer, comprising at least one vinyl monomer on B.2a 95 to 5 wt.%, preferably 80 to 8 wt.%, in particular 70 to 9 wt.%, based on the graft polymer, one or more rubber-elastic graft bases with glass transition temperatures < -50°C, more preferably < -60°C, particularly preferably < -70°C.

10. Thermoplastic composition according to any one of claims 1 to 9, characterized in that the composition comprises at least one additive (Ila) to (Iln) in the specified amounts. 0.05 to 10 parts by mass (Ila) of the UV absorber, 0.001 to 5 parts by mass (Ilb) of the sterically hindered amine light stabilizer, 0.1 x 10"5 up to 2x 10" 4 Mass components (IIc) of the bluing agent, 0.001 to 1 part by mass (Ild) of the antioxidant, 0.0001 to 2 parts by mass (Ile) of the sliding and demolding agent, 0.00001 to 1 part by mass (1lf) of the acidic additive, 0.05 to 5 parts by mass (Ilg) of the OH and acid group scavenger, 0, 1 x IO 7 up to 1 x IO 3 Mass fractions (Ilh) of the alkaline compound, 0, 1 x IO 7 up to 1 x IO 3 (Ili) Mass fractions of the reducing agent, 0.001 to 2 parts by mass (Ilj) of the antistatic agent, 0.001 to 5 parts by mass (Ilk) of the colorant, 1 to 100 parts by mass (III) of the inorganic filler, 0.01 to 30 parts by mass (Ilm) of the flame retardant and / or comprises 5 to 95 parts by mass (Iln) of the polymeric blend partner, where the mass units are each based on 100 mass units of component (I).2025PF30041 - Abroad 11. Thermoplastic composition according to any one of claims 1 to 10, wherein the copoly(ester) carbonate (I), 5 to 20 mol-% of the unit (B), 3 to 12 mol-% of unit (C) and comprising at least 65 mol% of the unit (A), where the mol% values ​​refer to the total amount of substance of units (A), (B), (C), where applicable (D) and where applicable units other than (A), (B), (C) and (D).

12. Thermoplastic composition according to any one of claims 1 to 11, wherein the copoly(ester) carbonate (I), 8 to 12 mol% of unit (B), 3.5 to 8.0 mol-% of unit (C) and comprising at least 80 mol-% of the unit (A), where the mol% values ​​refer to the total amount of substance of units (A), (B), (C), where applicable (D) and where applicable units other than (A), (B), (C) and (D).

13. Thermoplastic composition according to any one of claims 1 to 12, characterized in that the copoly(ester) carbonate (I) contains less than 8% end groups of formula (Y), (Y), where the position of formula (Y) marked with is the position at which the end group of formula (Y) is incorporated into the copoly(ester) carbonate and the % refers to the totality of the end groups.

14. Thermoplastic molding compound obtained from the thermoplastic composition according to any one of claims 1 to 13.

15. Molded bodies obtained from the thermoplastic molding compound according to claim 14.

16. Diphenyl ester of formula 2025PF30041 - Abroad 17. Diphenyl esters of the formula 18. Diphenyl esters of the formula 19. Mixture of substances containing at least two diphenyl esters selected from the diphenyl esters of claims 16 to 18.

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