Copoly(ESTER) carbonate stable against aqueous media and other chemicals and having good processability

Abstract

The invention relates to a copoly(ester) carbonate of defined units (A), (B) and (C) with defined amount proportions, wherein said structure and amount ratios cause the copoly(ester) carbonate to have excellent stability in aqueous media and also against other chemicals such as rapeseed oil, lipid solution or organic solvents. The present invention also relates to a composition containing the copoly(ester) carbonate according to the invention, a moulding containing the copoly(ester) carbonate according to the invention, and to a method for producing the copoly(ester) carbonate according to the invention.

Description

[0001] STABLE COPOLY(ESTER)CARBONATE WITH GOOD PROCESSABILITY AGAINST AQUEOUS MEDIA AND OTHER CHEMICALS

[0002] The present invention relates to a copoly(ester)carbonate composed of defined units (A), (B), and (C) in defined proportions. This structure and proportions result in the copoly(ester)carbonate exhibiting excellent stability in aqueous media and also against other chemicals such as rapeseed oil, lipid solutions, or organic solvents. The present invention also relates to a composition comprising the copoly(ester)carbonate according to the invention, a molded part comprising the copoly(ester)carbonate according to the invention, and a process for producing the copoly(ester)carbonate according to the invention.

[0003] Polyesters, polycarbonates, and polyestercarbonates are known to exhibit good mechanical properties, heat resistance, and weathering resistance. Each polymer group exhibits certain key characteristics, depending on the monomers used, that distinguish such materials. Polycarbonates, for example, exhibit particularly good mechanical properties, whereas polyesters often exhibit better chemical resistance. Depending on the monomers selected, polyestercarbonates exhibit property profiles from both of these groups. Depending on the choice of reactants, (co)polycarbonates, (co)polyesters, or copoly(ester)carbonates can be formed.

[0004] While aromatic polycarbonates or polyesters often have a good property profile, they exhibit weaknesses in terms of aging and weathering resistance. For example, UV light absorption leads to yellowing and possibly embrittlement of these thermoplastic materials. Aliphatic polycarbonates and polyester carbonates exhibit better properties in this regard, 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 slightly increase the glass transition temperatures.

[0005] The polyesters obtainable by the reaction of cyclohexanedicarboxylic acid and isosorbide are described by Oh et al. in Macromolecules 2013, 46, 2930-2940. However, these polymers have the disadvantage of interacting with hot water. Such polymers absorb water and swell. This drastically changes the polymer morphology. For example, transparency is completely lost. This drastically limits the potential applications of such polyesters. Im et al. showed that the aforementioned polyesters made from cyclohexanedicarboxylic acid and isosorbide exhibit structural deformations upon contact with hot water (Im et al., RSC Adv. 2017, 7, 6315, Structural deformation phenomenon of synthesized poly(isosorbide-1,4-cyclohexanedicarboxylate) in hot water).It has been shown (see comparative examples of the present invention) that copoly(ester)carbonates based on isosorbide and cyclohexanedicarboxylic acid, as described, for example, in EP3026074, also interact with water in principle. The change in polymer morphology in hot water is also drastic. This limits the use of such polymers in hot, humid climates.

[0006] Terephthalic acid-based polyesters are known to exhibit high stability against water and hydrolysis. However, Duchateau et al. in Biomacromolecules, 2008, 9, 3090-3097 (Incorporation of Isosorbide into Poly(butylene terephthalate via solid state polymerization)) demonstrated that polyesters made from isosorbide, terephthalic acid, and other diols lack thermal stability. Such polyesters exhibit significant weight loss in TGA measurements below 300 °C. However, thermal stability is of great importance for conventional polycarbonate applications. Furthermore, systems containing aromatic monomers are not sufficiently resistant to UV radiation.

[0007] Polycarbonates made from isosorbide and cyclic diols are described in EP2033981. These polycarbonates exhibit good mechanical properties, but sometimes limited stability against aqueous media (see comparative examples of the present invention). Furthermore, they exhibit glass transition temperatures above 100°C. However, to achieve good mechanical properties, a certain proportion of cyclic diol from fossil raw materials is necessary. This proportion is usually greater than 20%, which reduces the proportion of bio-based monomers in the polymer backbone. Furthermore, these aliphatic polycarbonates cannot be processed at high temperatures without decomposition. Thus, these special aromatic polycarbonates cannot be processed and used like conventional polycarbonates. Processing temperatures for conventional aromatic polycarbonates in injection molding are usually approximately 150°C above the glass transition temperature.For a polycarbonate made from approximately 70% isosorbide and 30% cyclohexanedimethanol, the glass transition temperature is approximately 120 °C, making the processing temperature relatively close to the decomposition range. This illustrates that these polymers are limited not only by their lack of resistance to solvents and potentially other chemicals, but also in terms of processing.

[0008] Polyesters made from isosorbide, terephthalic acid, and other monomers such as cyclohexanedimethanol are described in EP2478031. These materials are extremely stable against aqueous media. However, these polyesters contain aromatic dicarboxylic acids—particularly terephthalic acid. Here, too, the use of aromatic structural units makes such materials unsuitable for outdoor use without appropriate protection, such as a coating.

[0009] Copolycarbonates and copolyestercarbonates 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 only being partially transparent. They are usually cloudy or opaque. Furthermore, it has been shown that these polymers have a high melt viscosity (see comparative examples of the present invention). However, a high melt viscosity is disadvantageous with regard to processability. In particular, a high melt viscosity is disadvantageous because aliphatic polycarbonates or polyestercarbonates do not have the high processing temperatures of the corresponding aromatic poly- and polyestercarbonates. Non-transparent or highly cloudy materials can be used for optical applications such as lighting applications or for applications in the pharmaceutical sector, such asin Luer lock valves, stopcocks, and other IV connectors, they are used only to a limited extent or not at all. This makes it impossible to simply serve traditional applications of aromatic polycarbonates with such aliphatic polymers. Furthermore, such polymers exhibit lower surface hardness (see comparative examples of the present invention). As a result, they are prone to scratching and cannot be used in unpainted outdoor applications.

[0010] EP2840102 describes polymers with low water absorption, good heat resistance, and low-temperature toughness. These polycarbonates or copoly(ester)carbonates contain blocks of certain oligocarbonates made from diols or certain blocks made from oligoesters. Polyestercarbonates with long-chain diols or diacids with more than 12 carbon atoms are not specifically described. Properties such as behavior during storage in hot water are not discussed. Example 19 of EP2840102 describes an isosorbide-containing copoly(ester)carbonate containing an ester block made from terephthalic acid and cyclohexanedimethanol. However, the polymer has only a small proportion (<50 mol%) of bio-based monomers (isosorbide) and a low glass transition temperature (approx. 100 °C).

[0011] The state of the art provides some suggestions for improving specific individual properties of polycarbonates or copoly(ester)carbonates. However, there is a lack of teaching on how to positively influence several of these properties simultaneously. In particular, there is a lack of teaching on how to provide polymer structures that eliminate at least one of the disadvantages described above and, at the same time, could serve as a replacement for the established aromatic polycarbonates in terms of processability.

[0012] Based on this prior art, the present invention was therefore based on the object of eliminating at least one, preferably several, of the disadvantages described above. In particular, the invention was based on the object of providing a polymer structure which has high stability against water, in particular hot water. At the same time, the polymer structures should be intrinsically weather-stable, in particular intrinsically UV-resistant, and thus suitable for outdoor applications. Likewise, in particular at the same time, a polymer structure should be provided which has high scratch resistance. Furthermore, the polymer structure should preferably also have high resistance to chemicals such as solvents and / or lipid solutions and particularly preferably also high fat resistance, in particular rapeseed oil resistance.The resulting polymer structure should therefore preferably simultaneously exhibit high hot water resistance, good grease resistance, and good processability, particularly preferably comparable to that of conventional aromatic polycarbonates (e.g., based on bisphenol A), as well as high scratch resistance. At the same time, the polymer structure should preferably be intrinsically weather-resistant.

[0013] Likewise, a preferred object of the present invention was to provide a polymer structure that exhibits good thermal stability. In particular, it was an object to achieve thermal stability comparable to that of conventional aromatic polycarbonates. Likewise, preferably at the same time, it was an aim to provide polymer structures that can serve the same range of applications as conventional polycarbonates. Thus, the polymer structure should preferably exhibit high glass transition temperatures, in particular above 110°C, preferably above 120°C. Likewise, it is preferably required for this that the polymer structures have a sufficiently high molecular weight to exhibit appropriate mechanical properties, in particular ductility in an unnotched impact test at room temperature.In this case, “a polymer with a sufficiently high molecular weight” is preferably understood to mean a polymer which has a relative solution viscosity above 1.20, preferably 1.21 to 1.65, more preferably 1.22 to 1.63, particularly preferably from 1.23 to 1.62 and very particularly preferably from 1.26 to 1.55, each measured in dichloromethane at a concentration of 5 g / l at 25 °C using an Ubbelohde viscometer.

[0014] At least one, preferably all, of the above-mentioned objects have been achieved by the present invention. Surprisingly, it has been found that polyester carbonates or polycarbonates obtained from 1,4:3,6-dianhydrohexitol, specific cycloaliphatic diols, especially TCD-dimethanol, and long-chain diols or long-chain dicarboxylic acids fulfill at least one, preferably all, of the above-mentioned objects.

[0015] According to the invention, a copoly(ester)carbonate is provided, comprising the units (A), (B), (C), optionally (D) and optionally units different from (A), (B), (C) and (D), where each r and each s independently represents a number between 0 and 4, and each R 1 independently represents a structure of the formulas (RIA), (RIB), (R1C) or (R1D) where a is 0 or 1, marked positions in formulas (RIA) to (R1D) are the positions where the (CH2) shown in formula (B) r -group or (CH2)s-group, and

[0016] (C), where both t are independent of R 2 are either 0 or 1 at the same time and each R 2 independently of one another represents an aliphatic group having 16 to 44 carbon atoms, which may contain one or more double bonds, wherein at least partially direct links are present between the units (A), (B), (C), optionally (D) and optionally units other than (A), (B), (C) and (D), wherein, if there is a direct link between at least two of the units selected from the group consisting of (A), (B), (C) and optionally (D), the position of the units (A), (B), (C), (D) marked with is then linked to the position of these units marked with, with the exception that when t in formula (C) is 0, no direct link between two units with each other, if t in formula (C) is 0, there is no direct link between unit (C) and unit (D) and there is no direct link between two units (D) with each other, wherein the copoly(ester)carbonate comprises 4 to 25 mol% of unit (B), 2 to 14 mol% of unit

[0017] (C), 0 to 5 mol% of unit (D) and at least 55 mol% of unit (A), where the mol% data refer to the total amount of units (A), (B), (C), if appropriate

[0018] (D) and, where appropriate, units different from (A), (B), (C) and (D).

[0019] Surprisingly, it was found that with the polymer structure according to the invention, good property profiles can be achieved even with predominantly aliphatic building blocks. As described above in the prior art, almost all aliphatic polyesters or copoly(ester)carbonates, which are amorphous, lack stability towards water. In contrast, polyesters consisting of aromatic building blocks, such as terephthalic acid, with regard to the acid component, are usually stable towards water. However, these, in turn, lack UV and weathering stability. The polymer structure according to the invention surprisingly provides copoly(ester)carbonates which exhibit both good stability towards water, preferably hot water stability, and good grease resistance, as well as good resistance to lipid solutions and organic solvents, with good processability and good UV and weathering stability.Likewise, the copoly(ester)carbonates 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 polymers according to the invention are suitable for outdoor applications. This is particularly true without the need for additional coating, since their scratch resistance is high. This is particularly surprising since copoly(ester)carbonates with the same monomer units but different proportions of these monomer units do not exhibit these properties. Likewise, copoly(ester)carbonates that contain one less unit of the defined units (A), (B), and (C) do not exhibit this property profile. However, the above-mentioned property profile of the copoly(ester)carbonates according to the invention means that they can be used, for example, in the pharmaceutical sector (contact with aggressive pharmaceuticals).At the same time, although they are essentially composed of aliphatic building blocks, they have high glass transition temperatures of at least 110 °C, preferably 120 °C. At the same time, they also have good processability. They have such a melt viscosity that they can be easily processed, for example, by injection molding, without decomposition (due to their good thermal stability). This makes them almost as processable as classic aromatic polycarbonates and thus at least the classic areas of application of classic aromatic polycarbonates can be served. At the same time, the copoly(ester)carbonates according to the invention can have a high proportion of bio-based monomers, since at least units (A) and (C) can be obtained from bio-based monomers. Likewise, the copoly(ester)carbonates according to the invention have such a high molecular weight that it is ensured that the resulting mechanical properties are sufficient, i.e.for example, ductility is present in an unnotched impact test at room temperature. In particular, the copoly(ester)carbonates of the invention can also be produced using processes that do not require the handling of challenging feedstocks, especially phosgene. This also makes the copoly(ester)carbonates of the invention and their production process advantageous from both an ecological and economic perspective.

[0020] The invention relates to "copoly(ester)carbonates." The brackets are preferably to be understood as meaning that the invention encompasses "copolycarbonates or copolyestercarbonates." The skilled person is able to recognize when the polymer of the invention contains ester groups or not. This depends in particular on whether both "t"s in unit (C) are 1 (in which case a polycarbonate is formed) or 0 (in which case a copolyestercarbonate is formed).

[0021] The copoly(ester)carbonate according to the invention comprises the unit (A), with where the positions marked with # and * are the positions with which the unit (A) is incorporated into the copoly(ester)carbonate. Preferably, formula (A) is represented by formula (A*) with where n represents the average number of repeating units, and the positions marked with # and * have the meanings given for (A). Particularly preferably, n is greater than 1. Very particularly preferably, n is greater than 1 to 200, and especially preferably, n is greater than 1 to 100. This means that unit (A) can also be present as a block of several directly linked units (A). The copoly(ester)carbonate according to the invention particularly preferably has direct links between at least two units (A).

[0022] In the context of the present invention, the term "average number of repeat units" is known to the person skilled in the art. The person skilled in the art knows how to determine this parameter. In particular, this parameter can be determined by means of Maldi-TOF, GPC and / or 'FI-NMR and / or 13 C-NMR. In particular in 'H-NMR and / or 13C-NMR can show that the “end groups” of possible blocks (i.e. preferably when a block is present with direct links between the same units, this block has end groups at the beginning and end which have direct links to units which are different from the units in question) can provide information about the average number of repeating units. It is also clear that the number of repeating units (i.e. preferably 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. In addition, the person skilled in the art is 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 at a high molar percentage in the copoly(ester)carbonate according to the invention will be more likely to be bonded to another structure of the same type than a structure present only at a low molar percentage. The skilled person is aware that the upper limit of the average number of repeating units should at most be so high that all structures of the same type are condensed into one block. Preferably, (A) or (A*) is selected from at least one of the structures (A1), (A2) and (A3), where , where the positions marked with # and * have the meanings given for (A) and corresponding brackets are present for formula (A*). Very particular preference is given to (A) or (A*) being represented by formula (A1) (if appropriate with corresponding brackets for formula (A*)). It will be apparent to those skilled in the art that these 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, which entails all the advantages of a bio-based monomer and the resulting polymer (e.g., better sustainability, as it is obtainable from renewable raw materials). Unit (A) or (A*) particularly preferably consists of unit (A1). Very particular preference is given to unit (A) or (A*) being bio-based.

[0023] Furthermore, the copoly(ester)carbonate according to the invention comprises the unit (B), wherein 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 represents a structure of the formulas (RIA), (R1B), (R1C) or (R1D) where a is 0 or 1, preferably 0, where b is 0 or 1, preferably 0, , w The marked positions in formulas (RIA) to (RID) are the positions where the (CH2) shown in formula (B) r -group or (CH2) S -group and where the positions marked with # and * are the positions with which the unit (B) is incorporated into the copoly(ester)carbonate.

[0024] It is clear that in unit (B) more than one of the units (RIA), (RIB), (R1C) or (R1D) can be present.

[0025] It is preferred that unit (B) is represented by formula (B*) with

[0026] (B*), where m stands for the average number of repeating units and the positions marked with # and * have the meanings given for (B). This is particularly preferred if unit (A) also stands for unit (A*). Particularly preferably, m is greater than 1. Very particularly preferably, m is greater than 1 to 80, especially preferably, m is greater than 1 to 50, and very particularly preferably, m is greater than 1 to 10.

[0027] 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 1independently of one another for a structure of the formulas (RIA). In particular, it is preferred that r and s in formulas (B) and (B*) are 1 and R 1 in formulas (B) and (B*) represents the structure of formula (RIA). Most preferably, unit (B) or (B*) is represented by unit (Bl), where (Bl), where the ones marked with # and *

[0028] Positions that have the meanings given for (B). Very particularly preferably, unit (B) consists of unit (B1). It will be apparent to the person skilled in the art that this unit (B1) is a unit derived from TCD-dimethanol (also referred to as TCD-alcohol, tricyclodecanedimethanol, or [8-(hydroxymethyl)-3-tricyclo[5.2.1.0 2,6]decanyl]methanol). TCD-dimethanol is generally present as an isomer mixture. Up to 32 isomers are possible. Depending on the reaction conditions of the polymerization, the initial number and / or types of isomers in the monomer can also change in the resulting polymer. With particular preference, unit (B1) is obtained from a mass-balanced TCD-dimethanol. This has the particular advantage that the CCE footprint of the copoly(ester)carbonate according to the invention can thus be reduced.

[0029] The copoly(ester)carbonate according to the invention further comprises the unit (C), wherein where both t are independent of R2 are either 0 or 1 at the same time and each R 2 independently of one another represents an aliphatic group having 16 to 44 carbon atoms, which optionally contains one or more double bonds, and wherein the positions marked with # and * are the positions with which the unit (C) is incorporated into the copoly(ester)carbonate. Particularly preferably, each R 2independently of one another represent an aliphatic group having 17 to 44 carbon atoms, particularly preferably having 18 to 44 carbon atoms, particularly preferably having 19 to 44 carbon atoms, particularly preferably having 20 to 44 carbon atoms, particularly preferably having 21 to 44 carbon atoms, particularly preferably having 22 to 43 carbon atoms, particularly preferably having 23 to 42 carbon atoms, particularly preferably having 24 to 41 carbon atoms, particularly preferably having 25 to 40 carbon atoms, particularly preferably having 26 to 39 carbon atoms, particularly preferably having 27 to 38 carbon atoms, particularly preferably having 28 to 37 carbon atoms, particularly preferably having 29 to 37 carbon atoms, particularly preferably having 30 to 37 carbon atoms, particularly preferably having 31 to 37 carbon atoms, particularly preferably having 32 to 37 carbon atoms and very particularly preferably having 33 to 37 carbon atoms.

[0030] In the context of the present invention, the term “aliphatic” or “aliphatic group”, unless defined otherwise, refers to a hydrocarbon group which does not contain any aromatic units. However, this group may have one or more double bonds. Furthermore, this group may have one or more cycles. These cycles may be condensed with one another (i.e., for example, one or more carbon atoms may belong to two cycles) or be linked to one another by, for example, alkylene groups or alkylidene groups. This one or more cycles may have one or more double bonds. However, it should be noted that, according to the invention, aromatic cycles are not encompassed by the definition of “aliphatic”. Furthermore, the one or more cycles or the aliphatic group itself may be interrupted by one or more heteroatoms. However, this is less preferred.

[0031] In the context of the present invention, the term "alkyl" or "alkyl group" preferably refers, unless otherwise stated, to an alkane structure from which a 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 in the present invention.

[0032] In the context of the present invention, the term "alkylene" or "alkylene group" preferably refers, unless otherwise stated, 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 removed from any carbon atoms in the alkane structure. This means that the two carbon atoms can be adjacent, but do not necessarily have to be adjacent. 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 linked to the rest of the molecule via two single bonds.The alkylene group preferably comprises methylene, ethylene, n-propylene, isopropylene, 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-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.In addition, the alkylene group according to the present invention may optionally contain at least one carbonyl group, optionally contain 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. In addition, the term "cycloalkylene group" is also used according to the invention. The above-mentioned statements apply here, with the addition that the group may additionally contain one or more cycles. These cycles can be condensed with each other (i.e., one or more carbon atoms can belong to two cycles) or can be connected to each other, for example, by alkylene groups. This one or more cycles can contain 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.

[0033] In the context of the present invention, the term "alkylidene" or "alkylidene group" preferably refers, unless otherwise stated, 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. The alkylidene group preferably comprises isopropylidene, n-propylidene, isoheptylidene, and the like.

[0034] In the context of the present invention, the term "aralkyl" preferably refers, unless otherwise stated, to a linear, cyclic, or branched alkyl group that is mono-, di-, or polysubstituted by aryl radicals. In the context of the present invention, the term "aryl" preferably refers, unless otherwise stated, to an aromatic hydrocarbon radical. Examples of "aryl" are phenyl, o-, p-, and m-toluyl, naphthalene, phenanthryl, or anthranyl.

[0035] In the context of the present invention, the term "alkoxy" or "alkoxy group" preferably refers, unless otherwise stated, to a linear, cyclic, or branched alkyl group that is singly bonded to an oxygen atom (-OR). Alkoxy groups according to the present invention preferably have 1 to 6 carbon atoms. Particularly preferably, alkoxy groups include methoxy, ethoxy, α-propoxy, iso-propoxy, n-butoxy, and sec-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. Based on the above definitions, the person skilled in the art will be able to understand further definitions not explicitly mentioned above.

[0036] According to the invention, it is preferred that R 2in formula (C) is represented by the following formula (R2A) with

[0037] CH3

[0038] R 11

[0039] - R 11 — Y— R 11 -

[0040] R 11 CH ' 3 (R2A), where Y is a bridging structure selected from the group consisting of an alkylene group having 1 to 4 carbon atoms, an alkylidene group having 1 to 4 carbon atoms and a cycloalkylene group having 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms, where the cycloalkylene group optionally contains one or more double bonds and / or is optionally condensed to one or more further cycloalkylene groups, where the one or more further cycloalkylene groups optionally each have one or more double bonds, where the R adjacent to the bridging structure 11-groups are bonded to any position of the bridging structure and where each R 11 independently of one another represents an alkylene group having 1 to 12 carbon atoms or an alkylidene group having 1 to 12 carbon atoms, with the proviso that the structure of formula (R2A) comprises 16 to 44 carbon atoms and wherein the positions marked with , in formula (R2A) are the positions at which the (O)t groups shown in formula (C) are located.

[0041] Particularly preferably, the formula (R2A) is represented by one of the formulas (R2Aa), (R2Ab), (R2Ac) or (R2Ad), with where each R 11 and every has the meanings given for (R2A), the cycle of formula (R2Ac) optionally has one or two double bonds, and each cycle of formula (R2Ad) independently of one another optionally contains one or two double bonds. It is also particularly preferred that R 2in formula (C) is represented by 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 the formula (R2Aa)).

[0042] 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 involve the formation of an aromatic ring. As explained further below, it may be that when R 2 in formula (C) comprises a mixture of at least two different formulas (R2Aa), (R2Ab), (R2Ac), and (R2Ad), small amounts of aromatic bridging structures Y according to formula (R2A) are also present. However, this is less preferred.

[0043] Particularly preferred is each R 11in the formula (R2A) and / or in the formulas (R2Aa), (R2Ab), (R2Ac) or (R2Ad) independently of one another represent an alkylene group having 1 to 10 carbon atoms, with the proviso that the structure of the formula (R2A) and / or in the formulas (R2Aa), (R2Ab), (R2Ac) or (R2Ad) comprises 16 to 44 carbon atoms.

[0044] It is also preferred that the R 2 , (R2A), (R2Aa), (R2Ab), (R2Ac) and / or (R2Ad) in the unit (C) has 21 to 44 carbon atoms. It is equally preferred that the group represented by R 2, (R2A), (R2Aa), (R2Ab), (R2Ac) and / or (R2Ad) in the unit (C) has 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 most preferably 33 to 37 carbon atoms.The person skilled in the art is able to transfer this limited number of carbon atoms to the above-mentioned provisions regarding the number of carbon atoms.

[0045] 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.

[0046] The unit (C) according to the invention is very particularly preferably obtained by condensing dimer fatty acid and / or a dimer diol obtained by reducing dimer fatty acid.

[0047] It is known to those skilled in the art that dimer fatty acid is a mixture of different acids.

[0048] The predominant structures look like this.

[0049]

[0050] Fully hydrogenated compounds are preferred. Dimer fatty acids are generally a mixture. They are produced by condensing various unsaturated fatty acids. A fatty acid with conjugated double bonds (conjuenic acid) is reacted with other unsaturated fatty acids. Conjugated linoleic acids are particularly preferred for this purpose. The reaction usually takes place via Diels-Alder addition, forming a partially unsaturated C6 ring. Thus, dimer fatty acids initially comprise at least some of one or more double bonds. In addition to the dimer, the mixture of dimer fatty acids can also comprise trimers and monomers of the fatty acids. Oleic acid and linoleic acid are particularly preferred for the reaction. The double bonds contained in the dimer fatty acid are generally hydrogenated.To obtain a dimer diol obtained by reducing dimer fatty acids, the acid groups are reduced to the corresponding alcohol groups. This is a process known to those skilled in the art. With regard to the unit of formula (C), it should be noted that this reduces the total number of carbon atoms in the R group. 2 for dimer fatty acid and for a dimer diol obtained by reduction of dimer fatty acid, even if the same dimer fatty acid is used in both cases. In the case where the dimer fatty acid has 36 carbon atoms, R 2 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) present (at the respective end of the units marked with *). If the same dimer fatty acid with 36 carbon atoms is reduced to a dimer diol, the R 2According to unit (C), it has 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 clear how this can be applied to all units encompassed by unit (C).

[0051] Most preferably, the unit (C) according to the invention is obtained by condensing dimer fatty acid having 36 carbon atoms and / or a dimer diol having 36 carbon atoms obtained by reducing dimer fatty acid.

[0052] Dimer fatty acids are commercially available and are 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 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 orDimerdiol is a purified mixture comprising predominantly diacid or diol with 36 C atoms.

[0053] Unit (C) can be a bio-based unit, which offers all the advantages of a bio-based monomer and the resulting polymer (e.g., greater sustainability, as it is made from renewable raw materials). Unit (C) is most preferably bio-based.

[0054] Furthermore, a unit of formula (D) may be present in the copoly(ester)carbonate according to the invention, with 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 only present in the copoly(ester)carbonate according to the invention to a maximum of 5 mol% (where mol% data relate to the total amount of the units (A), (B), (C), optionally (D) and optionally units other than (A), (B), (C) and (D)). The unit (D) is particularly preferably present in the copoly(ester)carbonate according to the invention to a maximum of 0 mol%, particularly preferably from 0 to 3 mol%, further preferably from 0.01 to 2 mol% and very particularly preferably 0 mol%.

[0055] Unit (D) can be formed by condensing cyclohexanedicarboxylic acid into the copoly(ester)carbonate of the invention. However, it has been found that an excessively high molar proportion of unit (D) in the copoly(ester)carbonate of the invention leads to a deterioration in hot water resistance. Therefore, it is preferable to keep the proportion of unit (D) in the copoly(ester)carbonate of the invention as low as possible.

[0056] The copoly(ester)carbonate according to the invention has at least some direct links between the units (A), (B), (C), optionally (D) and optionally units different from (A), (B), (C) and (D). In this way, it is apparent to the 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 linkage" is preferably understood to mean that the stated units are directly linked to one another. This is preferably achieved by having no further unit between the stated units. For example, a unit (A) can have a direct link to a unit (B) in that the position marked with * of unit (A) is directly bonded to the position marked with # of unit (B) to form a carbonate group.According to the invention, it is specified that if there is a direct link between at least two of the units selected from the group consisting of (A), (B), (C) and optionally (D), the position of the units (A), (B), (C), (D) marked with "*" is then linked to the position of these units marked with "#", with the exception that if t in formula (C) is 0, there is no direct link between two units (C) with one another, if t in formula (C) is 0, there is no direct link between the unit (C) and the unit (D) and there is no direct link between two units (D) with one another. The expression “at least two units” in this formulation is to be understood as also encompassing direct links between more units, such as direct links (A)-(B)-(C), (A)-(A)-(B)-(C), (A)-(C)-(B)-(B), etc. The above-described property profile according to the invention is achieved by these direct links.

[0057] The exception why, when t in formula (C) is 0, there is no direct linkage between two units (C) to one another, when t in formula (C) is 0, there is no direct linkage between unit (C) and unit (D), and why there is no direct linkage between two units (D) to one another, is obvious to the person skilled in the art. Unit (C), when t in formula (C) is 0, or unit (D) are obtained by incorporating dicarboxylic acids into the copoly(ester)carbonate. This necessarily results in the formation of ester groups. Other corresponding linkages of these units are preferably not possible according to the invention.

[0058] In principle, the positions marked with # or * indicate the positions at which the respective unit or structure is incorporated into the copoly(ester)carbonate according to the invention. It is clear that these positions do not represent a "group" but merely serve to simplify the representation. To clarify: if, for example, a unit (A) has a direct link to a unit (B), the position marked with * in unit (A) is the oxygen atom next to the position marked with # in unit (B), so that a carbonate group is formed. This is transferable to all other units by the person skilled in the art.Since the invention relates to a copoly(ester)carbonate, the units (A), (B), (C) and optionally (D) form carbonate groups in the direct linkage with one another (and optionally ester groups if the unit (C) is included in the direct linkage and t is 0 in each case or if unit (D) is present). However, the copoly(ester)carbonate according to the invention provides that only positions marked with # are directly linked to positions marked with *. Furthermore, in the copoly(ester)carbonate according to the invention, there is no direct linkage between two units (C) if t in formula (C) is 0. Likewise, there is no direct linkage between unit (C) and unit (D) if t in formula (C) is 0. Furthermore, there is no direct linkage between two units (D) with one another.If there are direct links between two units (A) or direct links between two units (B), this can also be expressed using the units (A*) or (B*), where the integers n and m express the number of direct links.

[0059] It is particularly preferred that the copoly(ester)carbonate according to the invention has direct linkages between units (A) and (C) and, at the same time, both t in unit (C) are simultaneously 0. As a result, a group is preferably present in which a dianhydrohexitol group is directly linked via an ester group to, for example, a group derived from dimer fatty acid.

[0060] The copoly(ester)carbonate according to the invention preferably comprises structures of the unit (ABC)

[0061] (ABC), where n stands for 1, the mean number of repeat units or the preferences described above, R 1, r and s have the meanings given for (B*) in all preferences and combinations and m stands for 1, the average number of repeating units or the preferences described above, and t and R 2for the meanings given for unit (C) in all preferred and possible combinations. It will be apparent to the person skilled in the art that this unit (ABC) can be encompassed by the polymer and that further structures can optionally be present in the copoly(ester)carbonate according to the invention. Furthermore, the sequence of the monomers is preferably not specified. According to the invention, the copoly(ester)carbonate is preferably incorporated randomly. In this case, the structure (ABC) can also be present in only a small proportion in the copoly(ester)carbonate according to the invention because it reflects the specific sequence of individual structural elements. Due to certain process variants, differences in reactivity or the use of certain catalysts, the monomers may not be incorporated randomly; this is also preferably included in the generic unit (ABC).The copoly(ester)carbonate according to the invention preferably comprises structures in which direct linkages of the formulas (A)-(B), (A)-(C), (C)-(B), (A)-(B)-(C), (A)-(C)-(B), (A*)-(B), (A*)-(C), (A*)-(B)-(C), (A*)-(C)-(B), (A*)-(B*), (B*)-(C), (A*)-(B*)-(C), (A*)-(C)-(B*) or any desired mixtures of two or more of these structures are present.

[0062] It is preferred that the copolycarbonate according to the invention comprises unit (ABC*), where n stands for 1, the mean number of repeat units or the preferences described above, R 1 , r and s have the meanings given for (B*) in all preferences and combinations and m stands for 1, the average number of repeating units or the preferences described above, R 2has the meanings given for unit (C) in all preferences and possible combinations and o stands for 1, the average number of repeating units or a number between 1 and 5. It is obvious to the person skilled in the art that the structure (ABC*) shown above can be derived from the units (A), (B) and (C), where t in formula (C) is 1.

[0063] It is particularly preferred that the copoly(ester)carbonate according to the invention comprises unit (AC),

[0064] (AC), where n stands for 1 or the average number of repeating units and R 2 for the meanings set out for unit (C) in all preferences and possible combinations.

[0065] The copoly(ester)carbonate according to the invention particularly preferably comprises the unit (ABC) and (AC).

[0066] The copoly(ester)carbonate according to the invention is particularly preferably characterized in that it consists of at least 80% by weight, particularly preferably at least 85% by weight, likewise preferably at least 90% by weight of the units (A), (B), (C) and optionally (D). The copoly(ester)carbonate according to the invention therefore preferably has only small amounts of structures other than those of the units (A), (B) and (C). However, it should be noted that the end groups of the copoly(ester)carbonate according to the invention are preferably excluded. It is possible for the copoly(ester)carbonate according to the invention to also have functional units other than carbonate groups and optionally ester groups. However, it is further preferred for the copoly(ester)carbonate according to the invention to have no functional units other than carbonate and / or optionally ester groups. Here, too, the end groups can be excluded.This means that the maximum 20 wt.%, preferably maximum 15 wt.%, particularly preferably maximum 10 wt.%, which consist of units other than units (A), (B), (C) and optionally (D), can preferably be derived from other diols or dicarboxylic acids, which in turn lead to carbonate or ester groups by incorporation into the copoly(ester)carbonate.

[0067] 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% data relate to the total amount of units (A), (B), (C), optionally (D) and optionally units different from (A), (B), (C) and (D). It will be apparent to the person skilled in the art that these amounts can also relate to all preferences and combinations of preferences for the individual units (A), (B) and (C).

[0068] The copoly(ester)carbonate according to the invention particularly preferably comprises

[0069] 4 to 25 mol%, particularly preferably 5 to 20 mol%, equally preferably 7 to 18 mol%, very particularly preferably 10 to 15 mol% or very particularly preferably 8 to 12 mol% of unit (B),

[0070] 2 to 14 mol%, particularly preferably 3 to 12 mol%, very particularly preferably 3.5 to 7.0 mol% of unit (C) and at least 55 mol%, particularly preferably at least 65 mol%, likewise preferably at least 75 mol% and very particularly preferably at least 80 mol% of unit (A), where the mol% data relate to the total amount of units (A), (B), (C), optionally (D) and optionally units different from (A), (B), (C) and (D).

[0071] These molar ratios ensure that the copoly(ester)carbonate 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 against aqueous media, good hot water stability, good fat resistance, good resistance to lipid solutions and good solvent resistance.

[0072] The skilled person can determine the molar amounts of the various units in the copoly(ester)carbonate according to the invention. These can preferably be determined by means of 'H NMR spectroscopy. Depending on the process for preparing the copoly(ester)carbonate, it can be assumed that almost all of the monomers used react to form the polymer. In particular, the examples according to the invention showed that the molar ratios of the monomers are also reflected in the resulting polymer. This means that the skilled person can influence the molar ratios of the resulting units in the polymer by changing the molar ratios of the monomers used. It is also preferred that the defined mol % in the copoly(ester)carbonate according to the invention be determined by means of 'H NMR spectroscopy. This method is known to the skilled person.The copoly(ester)carbonate can, for example, be dissolved in CDCF, and the corresponding peaks of the structural units can be identified. Depending on the compounds used, the skilled person is able to assign these peaks to the structural units. The ratios and proportions can be determined using the integrals. On the other hand, the mol % according to the invention can also be determined using the amounts and ratios of the monomers used. It must be assumed that all monomers are fully incorporated into the copoly(ester)carbonate in the same ratio. This allows the skilled person to adjust the ratio in advance.

[0073] It is also possible to subsequently determine the molar ratios of the resulting units in the polymer using total evaporation. For this purpose, the polymer can be hydrolyzed, for example, under reflux with sodium methoxide. The resulting solution can then be acidified and evaporated to dryness. The residue can be dissolved in suitable organic solvents, and the compounds present can be analyzed by HPLC. The appropriate calibration and measurement using HPLC are known to those skilled in the art.

[0074] In addition to the units (A), (B), (C) and optionally (D), the copoly(ester)carbonate according to the invention can also have further units different from (A), (B), (C) and optionally (D). The copoly(ester)carbonate according to the invention preferably has unit (E), where

[0075] (E), where both z's, independently of x, are simultaneously either 0 or 1 and each x, independently of one another, represents a linear or branched alkylene group having 4 to 20, preferably 5 to 15 carbon atoms, which may optionally be interrupted by at least one heteroatom, a cycloalkylene group having 4 to 20, preferably 5 to 15 carbon atoms, which may optionally be interrupted by at least one heteroatom and where the cycloalkylene group may optionally contain multiple rings, or an aromatic group, and where the positions marked with # and * are the positions at which the unit (E) is incorporated into the copoly(ester)carbonate, with the exception that when z in formula (E) is 0, there is no direct linkage between two units (E) with one another. It is apparent to a person skilled in the art that this unit (E) must be different from the unit (D).Particularly preferably, x in unit (E) is an aromatic group, especially preferably an aromatic group having 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 formula (x1), (x2) or (x3), with.

[0076] (x3), where the marked positions in formulas (xl), (x2) and (x3) are the positions at which the (O) shown in formula (E) are located. z -groups. Particularly preferably, x in unit (E) is a structure of the formula (x1), (x2) or (x3), where both z are simultaneously 0.

[0077] The copoly(ester)carbonate according to the invention can also be branched. This can be influenced by the use of polyfunctional alcohols such as glycerol, trimethylolpropane, or tris(4-hydroxyphenyl)ethane (THPE), etc., or polyfunctional carboxylic acids such as citric acid, trimellitic acid, etc., in the synthesis of the copoly(ester)carbonate according to the invention.

[0078] The copoly(ester)carbonate according to the invention preferably comprises at most 25 mol%, particularly preferably at most 20 mol%, furthermore preferably at most 10 mol%, and very particularly preferably at most 5 mol% of aromatic groups. However, any end groups present are preferably excluded. It is preferred that unit (E) is present in the copoly(ester)carbonate according to the invention in an amount of at most 20 mol%, furthermore preferably at most 10 mol%, and very particularly preferably at most 5 mol%. It is particularly preferred that x in unit (E) is a structure of the formula (x1), (x2), or (x3), where both z's are simultaneously 0.

[0079] The copoly(ester)carbonate 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 according to the invention particularly preferably comprises end groups of the formula (Z)

[0080] (Z), where each R 7independently of one another represents hydrogen, an alkyl group having 1 to 34 carbon atoms, an aralkyl group having 7 to 34 carbon atoms, an aryl group having 6 to 34 carbon atoms, or a -COO-R' group, where R' represents an alkyl group having 1 to 34 carbon atoms, an aralkyl group having 7 to 34 carbon atoms, an aryl group having 6 to 34 carbon atoms, and each q independently represents 1 to 5, and the position marked with # is the position at which unit (Z) is attached to the copoly(ester)carbonate. It is evident that the position marked with # is attached to the position marked with * of the other units. Thus, the copoly(ester)carbonate according to the invention can have aromatic units as end groups. These do not adversely affect the intrinsic weathering stability of the polymer because their concentration is very low. Particularly preferably, q in unit (Z) is 1.R. is also preferred. 7 represents hydrogen or -COOCHs, most preferably hydrogen. The copoly(ester)carbonate according to the invention particularly preferably comprises end groups selected from the group consisting of the formula (Z), -OH, -COOH, and any mixtures of these groups. It is apparent to the person skilled in the art that formula (Z) encompasses, 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 the person skilled in the art.

[0081] It is further preferred that the copoly(ester)carbonate according to the invention is at least 50 mol%, more preferably at least 70 mol%, and most preferably at least 75 mol% bio-based. For the purposes of the present invention, the term "bio-based" is understood to mean that the chemical compound in question is accessible, obtainable, and / or preferably is such a renewable and / or regenerative raw material at the time of application. A renewable and / or regenerative raw material is preferably understood to mean a raw material that is regenerated by natural processes at a rate comparable to its degradation rate (see CEN / TS 16295:2012). The term serves in particular to distinguish it from raw materials made from fossil raw materials, 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 are lower in fossil raw materials. This can be done, for example, according to ASTM D6866-18 (2018) or ISO16620-1 to -5 (2015) or DIN SPEC 91236 2011-07. According to the invention, the term "biobased" is preferably used for compounds that have a C 14 Isotope content of over 0.1 x 10' 12 , particularly preferably over 0.2 x 10' 12 , and most preferably above 0.3 x 10 12 In particular, isosorbide and also dimer fatty acid or the dimer diol obtained by reduction of dimer fatty acid are bio-based.

[0082] The copoly(ester)carbonate according to the invention preferably has a relative solution viscosity above 1.20, particularly preferably from 1.21 to 1.65, further preferably from 1.22 to 1.63, especially preferably from 1.23 to 1.62, equally 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. The determination of the relative solution viscosity using an Ubbelohde viscometer is known to those skilled in the art. According to the invention, this is preferably carried out according to 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 (at least three measurements are always taken, and no more than nine). This is followed by the actual calibration with the solvent dichloromethane. The polymer sample is then weighed, dissolved in dichloromethane, and the flow time for this solution is determined three times. The mean of the flow times is corrected using the Hagenbach correction, and the relative solution viscosity is calculated.

[0083] This preferred relative solution viscosity ensures that the copoly(ester)carbonates according to the invention have sufficient mechanical properties. "Sufficient" is to be understood here as having mechanical properties comparable to those of conventional aromatic polycarbonates, in particular ductility in an unnotched impact test at room temperature. The invention further provides a composition comprising the copoly(ester)carbonate in all of the above-described embodiments, preferences, and combinations of preferences and one or more additives. The composition according to the invention is preferably thermoplastic. Likewise, the invention provides a molded part comprising the copoly(ester)carbonate in all of the above-described embodiments, preferences, and combinations of preferences or the composition according to the invention.

[0084] The polymer additives are preferably selected from the group consisting of flame retardants, anti-drip agents, flame retardant synergists, smoke inhibitors, lubricants and mold release agents, nucleating agents, antistatic agents, conductivity additives, stabilizers (e.g., hydrolysis, heat aging, and UV stabilizers, as well as transesterification inhibitors), flow promoters, phase compatibilizers, dyes and pigments, impact modifiers, and fillers and reinforcing agents. The composition according to the invention may also contain other thermoplastics that differ from the copoly(ester)carbonate according to the invention.The other thermoplastics are preferably materials based on polystyrene, styrene copolymers, aromatic polyesters such as polyethylene terephthalate (PET), PET-cyclohexanedimethanol copolymer (PETG), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), cyclic polyolefin, polybutylene succinate (PBS), poly- or copolyacrylates and poly- or copolymethacrylates, e.g. poly- or copolymethyl methacrylates (such as PMMA), polyamides (preferably polyamide 6 (PA6) and polyamide 6,6 (PA6,6)) and copolymers with styrene, e.g. transparent polystyrene-acrylonitrile (PSAN), thermoplastic polyurethanes, polymers based on cyclic olefins (e.g. TOPAS,® a commercially available product from Ticona) and mixtures of the polymers mentioned.

[0085] The compositions according to the invention can be prepared, for example, by mixing the copoly(ester)carbonate and the other constituents in a known manner and melt compounding and melt extruding them at temperatures of preferably 220°C to 300°C in conventional units such as internal kneaders, extruders, and twin-screw extruders. This process is generally referred to as compounding in the context of this application. The molded articles according to the invention can be produced, for example, by injection molding, extrusion, and blow molding processes. Another form of processing is the production of molded articles by deep drawing from previously produced sheets or films.

[0086] A compound of formula (I) is known, where where R 2 has the meanings given for formula (C) also in all preferences and combinations of preferences and each R 6independently represents hydrogen, an alkyl group having 1 to 34 carbon atoms, an aralkyl group having 7 to 34 carbon atoms, an aryl group having 6 to 34 carbon atoms or a -COO-R'- group, where R' represents an alkyl group having 1 to 34 carbon atoms, an aralkyl group having 7 to 34 carbon atoms, an aryl group having 6 to 34 carbon atoms and each x independently represents 1 to 5.

[0087] Particularly preferred is R 2 in formula (I) represents the formula (R2A) described in more detail above or the formulas (R2Aa), (R2Ab), (R2Ac) or (R2Ad) described above. It is preferred that x = 1 and R 6 represents hydrogen or -COOCHs. Formula (I) particularly preferably represents the diphenyl ester of the dimer fatty acid.

[0088] It has been found that this intermediate is particularly suitable for preparing copoly(ester)carbonates according to the present invention. Particular preference is given to using the compound of formula (I) for preparing the copoly(ester)carbonate according to the invention. Likewise, it is preferred that the compound of formula (I) be used for preparing a copoly(ester)carbonate, preferably the copoly(ester)carbonate according to the invention, by melt transesterification. The melt transesterification process is known per se to the person skilled in the art. Reference can be made, for example, to Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Volume 9, Interscience Publishers, New York, London, Sydney 1964. In the melt transesterification process, the starting materials are transesterified in the melt with the aid of suitable catalysts and, if appropriate, other additives.In particular, this is a process that can be carried out without solvents and / or phosgene. The compound of formula (I) can be formed either in situ during the melt transesterification process and / or formed beforehand and added as such as a reactant to the melt transesterification process.

[0089] Preferably, the compound of formula (I) can be obtained by a process comprising the reaction between a diacid HOOC-R 2 -COOH with a diaryl carbonate of formula (la):

[0090] (la), where x and R 6 have the meanings given for formula (I).

[0091] In a further aspect, the present invention relates to a process for preparing the copoly(ester)carbonate according to the invention, comprising at least the reaction of a 1,4:3,6-dianhydrohexitol, a diol of the formula (B2), at least one further compound selected from the group consisting of a diol of the formula (C2), a compound of the formula (C3) or any mixtures thereof and a carbonyl source, wherein where each r and each s independently represents a number between 0 and 4 and each R 1 independently represents a structure of the formulas (RIA), (RIB), (R1C) and (R1D) where a is 0 or 1, where the marked positions in formulas (RIA) to (R1D) are the positions where the (CH2) shown in formula (B2) r -group or (CH2)s-group, and where each R 2in formulas (C2) and (C3) independently of one another represents an aliphatic group having 16 to 44 carbon atoms, which may contain one or more double bonds, and each R 3 in formula (C3) independently of one another represent hydrogen, chlorine or -OR", where R" represents an aliphatic or aromatic radical. The copoly(ester)carbonate according to the invention is preferably prepared by the process according to the invention in all preferred forms and combinations of preferred forms. Likewise preferably, the copoly(ester)carbonate according to the invention is prepared by the process according to the invention.

[0092] The person skilled in the art is able to assign the structures of units (B2), (C2) and (C3) to the units (B) and (C) described above and to read into them the corresponding configurations, preferences and also combinations of preferences. The formula (C3) particularly preferably comprises the compound of formula (I) when R 3stands for "-OR". This includes all preferences and combinations of preferences.

[0093] The process according to the invention preferably comprises the reaction of up to 25 mol%, particularly preferably 5 to 20 mol%, likewise preferably 7 to 18 mol% and very particularly preferably 10 to 15 mol% or very particularly preferably 8 to 12 mol% of the compound (B2),

[0094] 2 to 14 mol%, particularly preferably 3 to 12 mol%, very particularly preferably 3.5 to 8.0 mol% of the compound (C2) and / or (C3) and at least 55 mol%, particularly preferably at least 65 mol%, likewise preferably at least 75 mol% and very particularly preferably at least 80 mol% of a 1,4:3,6-dianhydrohexitol, where the mol% data relate to the total amount of the 1,4:3,6-dianhydrohexitol, the compound (C2) and the compound (C2) and / or (C3).

[0095] According to the invention, up to 5 mol%, preferably up to 3 mol%, particularly preferably 0.01 to 2 mol% of cyclohexanedicarboxylic acid can also be used as a reactant. This leads to the formation of unit (D). However, this is less preferred for the reasons stated above.

[0096] The carbonyl source used in the process according to the invention can preferably be selected from phosgene and a diaryl carbonate of the formula (Ia),

[0097] (la), where each R 6independently of one another represents hydrogen, an alkyl group having 1 to 34 carbon atoms, an aralkyl group having 7 to 34 carbon atoms, an aryl group having 6 to 34 carbon atoms or a -COO-R' group, where R' represents an alkyl group having 1 to 34 carbon atoms, an aralkyl group having 7 to 34 carbon atoms, an aryl group having 6 to 34 carbon atoms and each x independently represents 1 to 5. The person skilled in the art will know that copoly(ester)carbonate can generally be produced by melt transesterification (see above) or by the interfacial process. The interfacial process is also fundamentally suitable, for example. B. from H. Schnell, Chemistry and Physics of Polycarbonates, Polymer Reviews, Vol. 9, Interscience Publishers, New York 1964 p. 33 ff. and on Polymer Reviews, Vol. 10, ''Condensation Polymers by Interfacial and Solution Methods'', Paul W. Morgan, Interscience Publishers, New York 1965, Chapter VIII, p.325 and the basic conditions are therefore familiar to the expert.

[0098] Both processes are encompassed by the process according to the invention. This is intended to mean, in particular, the expression "comprising at least the reaction." Depending on the process chosen, diols, optionally esters, preferably compounds of formula (I) react with diaryl carbonates of formula (Ia) (melt transesterification). Alternatively, phosgene is reacted with diols or acids at the phase interface between one or more organic solvents and water.

[0099] It is also clear to the person skilled in the art that, depending on the process used, the compound of formula (C3) is present as an ester, free acid or acid chloride.

[0100] The catalysts used for such processes are familiar to the person skilled in the art.

[0101] Description of the figure

[0102] Figure 1: 'H-NMR spectrum of the copolycarbonate of inventive example 17 in CDCE

[0103] Figure 2: 'H-NMR spectrum of the copolycarbonate of inventive example 16 in CDCE

[0104] The following embodiments describe specific combinations of the preferred embodiments. These are already covered by the general text above.

[0105] Embodiment 1: Copoly(ester)carbonate containing the units (A), (B), (C), optionally (D) and optionally units different from (A), (B), (C) and (D), with where each r and each s independently represents a number between 0 and 4, and each R 1 independently represents a structure of the formulas (RIA), (RIB), (R1C) or (R1D)

[0106] (R1B), where b is 0 or 1, g marked positions in formulas (RIA) to (RID) are the positions at which the (CFfijr group or (CFFf group) shown in formula (B) is located, and

[0107] (C), where both t are independent of R 2 are either 0 or 1 at the same time and each R 2 independently of one another represents an aliphatic group having 16 to 44 carbon atoms, which may contain one or more double bonds, wherein at least partially direct links are present between the units (A), (B), (C), optionally (D) and optionally units different from (A), (B), (C) and (D), wherein, if there is a direct link between at least two of the units selected from the group consisting of (A), (B), (C) and optionally (D), the position of the units (A), (B), (C), (D) marked with marked position of these units, with the exception that when t in formula (C) is 0, there is no direct linkage between two units (C) with each other, when t in formula (C) is 0, there is no direct linkage between unit (C) and unit (D) and there is no direct linkage between two units (D) with each other, wherein the copoly(ester)carbonate comprises 4 to 25 mol% of unit (B), 2 to 14 mol% of unit

[0108] (C), 0 to 5 mol% of unit (D) and at least 55 mol% of unit (A), where the mol% data refer to the total amount of units (A), (B), (C), if appropriate

[0109] (D) and, where appropriate, units different from (A), (B), (C) and (D).

[0110] Embodiment 2: Copoly(ester)carbonate according to embodiment 1, characterized in that the copoly(ester)carbonate is according to one of claims 2 to 10.

[0111] Embodiment 3: Copoly(ester)carbonate according to embodiment 1 or 2, characterized in that the copoly(ester)carbonate has direct links between at least two units (A).

[0112] Embodiment 4: Copoly(ester)carbonate according to one of embodiments 1 to 3, characterized in that unit (A) or (A*) consists of the unit (Al).

[0113] Embodiment 5: Copoly(ester)carbonate according to one of embodiments 1 to 4, characterized in that unit (A) or (A*) is bio-based.

[0114] Embodiment 6: Copoly(ester)carbonate according to one of embodiments 1 to 5, characterized in that each r and each s in unit (B) independently of one another represents a number between 0 and 4, preferably between 0 and 3, particularly preferably between 0 and 2, very particularly preferably 0 or 1.

[0115] Embodiment 7: Copoly(ester)carbonate according to one of embodiments 1 to 6, characterized in that in unit (B) each r and each s independently of one another represents a number between 0 and 2, very particularly preferably 0 or 1, and each R 1 independently represents a structure of formulas (RIA).

[0116] Embodiment 8: Copoly(ester)carbonate according to one of embodiments 1 to 7, characterized in that the unit (B) or (B*) consists of unit (B1).

[0117] Embodiment 9: Copoly(ester)carbonate according to one of embodiments 1 to 8, characterized in that each R 2in the unit (C) independently of one another represent an aliphatic group having 17 to 44 carbon atoms, particularly preferably having 18 to 44 carbon atoms, particularly preferably having 19 to 44 carbon atoms, particularly preferably having 20 to 44 carbon atoms, particularly preferably having 21 to 44 carbon atoms, particularly preferably having 22 to 43 carbon atoms, particularly preferably having 23 to 42 carbon atoms, particularly preferably having 24 to 41 carbon atoms, particularly preferably having 25 to 40 carbon atoms, particularly preferably having 26 to 39 carbon atoms, particularly preferably having 27 to 38 carbon atoms, particularly preferably having 28 to 37 carbon atoms, particularly preferably having 29 to 37 carbon atoms, particularly preferably having 30 to 37 carbon atoms, particularly preferably having 31 to 37 carbon atoms,particularly preferably having 32 to 37 carbon atoms and most preferably having 33 to 37 carbon atoms.,

[0118] Embodiment 10: Copoly(ester)carbonate according to one of embodiments 1 to 9, characterized in that (C) is present at least twice in the copoly(ester)carbonate and R 2 in the unit (C) stands for at least two different formulas (R2Aa), (R2Ab), (R2Ac) and (R2Ad).

[0119] Embodiment 11: Copoly(ester)carbonate according to one of embodiments 1 to 10, characterized in that the unit (C) is obtained by condensation of dimer fatty acid and / or a dimer diol obtained by reduction of dimer fatty acid.

[0120] Embodiment 12: Copoly(ester)carbonate according to one of embodiments 1 to 11, characterized in that the unit (C) is obtained by condensing dimer fatty acid having 36 carbon atoms and / or a dimer diol having 36 carbon atoms obtained by reducing dimer fatty acid.

[0121] Embodiment 13: Copoly(ester)carbonate according to one of embodiments 1 to 12, characterized in that unit (C) is bio-based.

[0122] Embodiment 14: Copoly(ester)carbonate according to one of embodiments 1 to 13, characterized in that the unit (D) is present in the copoly(ester)carbonate according to the invention in an amount of 0 to 5 mol%, particularly preferably 0 to 3 mol%, further preferably 0.01 to 2 mol% and very particularly preferably 0 mol%.

[0123] Embodiment 15: Copoly(ester)carbonate according to one of embodiments 1 to 14, characterized in that the copoly(ester)carbonate comprises the unit (ABC).

[0124] Embodiment 16: Copoly(ester)carbonate according to one of embodiments 1 to 15, characterized in that the copoly(ester)carbonate comprises the unit (AC).

[0125] Embodiment 17: Copoly(ester)carbonate according to one of embodiments 1 to 16, characterized in that the copoly(ester)carbonate consists of at least 80 wt.%, particularly preferably at least 85 wt.%, likewise preferably at least 90 wt.% of the units (A), (B), (C) and optionally (D).

[0126] Embodiment 18: Copoly(ester)carbonate according to one of embodiments 1 to 17, characterized in that the copoly(ester)carbonate has no functional units other than carbonate and / or optionally ester groups.

[0127] Embodiment 19: Copoly(ester)carbonate according to one of embodiments 1 to 18, characterized in that the copoly(ester)carbonate

[0128] 4 to 25 mol%, particularly preferably 5 to 20 mol%, equally preferably 7 to 18 mol% and very particularly preferably 10 to 15 mol% or very particularly preferably 8 to 12 mol% of unit (B),

[0129] 2 to 14 mol%, particularly preferably 3 to 12 mol%, very particularly preferably 3.5 to 8.0 mol% of the unit (C) and at least 55 mol%, particularly preferably at least 65 mol%, equally preferably at least 75 mol% and very particularly preferably at least 80 mol% of the unit

[0130] (A), wherein the mol% data refer to the total amount of the units (A), (B), (C), optionally (D) and optionally units different from (A), (B), (C) and (D).

[0131] Embodiment 20: Copoly(ester)carbonate according to one of embodiments 1 to 19, characterized in that the copoly(ester)carbonate has end groups of the formula (Z).

[0132] Embodiment 21: Copoly(ester)carbonate according to one of embodiments 1 to 20, characterized in that in the formula (Z) q = 1 and R 7 hydrogen or -COOCHs.

[0133] Embodiment 22: Copoly(ester)carbonate according to one of embodiments 1 to 21, characterized in that x in unit (E) is a structure of the formula (x1), (x2) or (x3), where both z are simultaneously 0.

[0134] Examples

[0135] Materials used:

[0136] Cyclohexanedicarboxylic acid: 1,4-Cyclohexanedicarboxylic acid; CAS 1076-97-7 99%; Tokyo Chemical Industries, Japan, abbreviated as CHDA.

[0137] Diphenyl carbonate: Diphenyl carbonate, 99.5%, CAS 102-09-0; Acros Organics, Geel, Belgium, abbreviated as DPC

[0138] 4-Dimethylaminopyridine: 4-(Dimethylaminopyridine; >98.0%; purum; CAS 1122-58-3; Sigma-Aldrich, Munich Germany, abbreviated as DMAP

[0139] Isosorbide: Isosorbide (CAS: 652-67-5), 99.8%, Polysorb PS A; Roquette Freres (62136 Lestrem, France); abbreviated as ISB

[0140] Lithium hydroxide monohydrate (CAS: 1310-66-3); >99.0%; Sigma-Aldrich

[0141] Terephthalic acid: (CAS: 100-21-0), 99+%, Acros Organics, Geel, Belgium

[0142] Tricyclodecanedimethanol: (CAS: 26896-48-0) ; mixture of isomers ; OQ Chemicals, 40789 Monheim, Germany

[0143] Dimer fatty acid: Pripol 1009 (CAS: 68783-41-5); Mn approx. 570 g / mol; hydrogenated, Croda, 41334 Nettetal, Germany

[0144] Sodium (2-ethyl)hexanoate: (CAS: 19766-89-3); 97%; Sigma-Aldrich, Munich, Germany

[0145] Dimerdiol: Pripol 2030 (CAS: 147853-32-5); Croda, 41334 Nettetal, Germany

[0146] Methyl tert-butyl ether (CAS: 1634-04-4); Azelis Deutschland GmbH, 53757 Sankt Augustin, Germany, abbreviated as MTBE

[0147] Methyl ethyl ketone (CAS: 78-93-3); Azelis Deutschland GmbH, 53757 Sankt Augustin, Germany, abbreviated as MEK

[0148] Isopropanol (CAS: 67-63-0); Azelis Deutschland GmbH, 53757 Sankt Augustin, Germany

[0149] Zeolite 4A: Sodium aluminum silicate (CAS: 1318-02-1)

[0150] Polycarbonate based on isosorbide and cyclohexanedimethanol 30:70 (CAS: 25037-45-0): manufactured according to EP2033981 Al; abbreviated as PCI 2-butyl-2-ethyl-l,3-propanediol (CAS: 115-84-4); 99.0%; Sigma-Aldrich, Munich

[0151] Germany, abbreviated as BEPD

[0152] Toluene (CAS: 108-88-3); 99%; Sigma-Aldrich, Munich, Germany

[0153] 2,2,4-Trimethylpentane or isooctane (CAS: 540-84-1); 99.5%; Sigma-Aldrich, Munich, Germany

[0154] Lipid solution: SmofKabiven central emulsion for infusion; qualitative and quantitative composition: 1000 ml contains: 508 ml amino acid solution with electrolytes, 302 ml 42% glucose solution, 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 acid-rich licorice oil 5.7 g.

[0155] Analytical methods:

[0156] Solution viscosity:

[0157] The relative solution viscosity (qrck, also referred to 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 to be measured through the Ubbelohde viscometer are measured 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 (at least three measurements are always taken, but no more than nine). This is followed by the actual calibration with the solvent dichloromethane. The polymer sample is then weighed, dissolved in dichloromethane, and the flow time is determined three times for this solution.The mean flow times are corrected using the Hagenbach correction, and the relative solution viscosity is calculated. Determination of the glass transition temperature:

[0158] The glass transition temperature was determined by differential scanning calorimetry (DSC) according to 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 transition temperature (Tg) measured as the inflection point in the second heating process.

[0159] Hot water resistance test:

[0160] 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 results were visually evaluated.

[0161] Deformation and fracture behavior under impact load without notch (Charpy impact test):

[0162] Impact bending test without and with 2 mm V-notch in the Charpy test at room temperature, carried out with a home-made drop tester from Polymer Physics with a drop mass of 1.86 kg, dome diameter of 20 mm, support diameter of 62 mm.

[0163] Chemical resistance test (lipid solution, isooctame toluene 1: 1):

[0164] At least two flat bars measuring 80 mm in length, 4 mm in height, and 10 mm in width were clamped in a circular template with a radius of 99 cm. This corresponded to an edge fiber strain of 2%. The surface of the bars was contaminated by continuous wetting with or complete immersion in the test medium. The time to fracture was measured. The measurement was stopped after 5–14 days.

[0165] Determination of shear rheology:

[0166] The measurement was performed on an ARES-G2 rheometer from TA. The oscillatory frequency sweep test in the range 0.001 Hz to 10,000 Hz was performed isothermally at 200°C, and the complex viscosity was derived from this.

[0167] Determination of scratch resistance:

[0168] 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 (hard metal ball) and a spring with a measuring range of 0-1 ON. The test bar was clamped in a carriage so that the set force acted on the test tip. The carriage, including the test bar, was set to IN and rolled 10mm over the surface to be tested. If no scratch marks were visually visible to two testers, the force was increased by 0.5N and the test was repeated. This was repeated until a visible scratch mark remained in the polymer. The highest force exerted is reported.

[0169] 'H-NMR spectroscopy:

[0170] The measurements were performed on a Bruker Avance NEO 600 MHz NMR spectrometer. The measurements were carried out in CDCl3. The samples contained isosorbide, tricyclodecane dimethanol, and dimerdiol or dimer fatty acid. The molar ratios of these components were evaluated as follows:

[0171] The respective characteristic signals of the monomers were integrated and “normalized” to the number of respective protons.

[0172] The evaluation of the polymers according to the invention in Examples 17 (with dimer diol) and 16 (with dimer fatty acid) is explained here by way of example. Reference is made to Figures 1 and 2.

[0173] 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 fractions is carried out as follows:

[0174] For the isosorbide content, the signals between 5.3 and 4.5 ppm were used.

[0175] The integral was set to “40” and corresponds to 4 protons of isosorbide.

[0176] The content of TCD-dimethanol and dimerdiol was determined from the signals between 4.2 and 3.8. This region contains 4 protons of isosorbide, 2 -CH2- groups of TCD-dimethanol (-O-CH2-), and 2 -CH2- groups of dimerdiol (-O-CH2-). Thus, 4 protons of TCD-dimethanol and 4 protons of dimerdiol are also located in this range.

[0177] The relative proportion of TCD-dimethanol could be determined from the range of 2.3 to 1.9 ppm. There are no protons of dimerdiol in this range. This range corresponds to approximately 4 protons of 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 of dimerdiol and 1 H of TCD-dimethanol. This resulted in the proportion of dimerdiol as 6.527 - 1.32 = 5.207, or 5.207 / 8.3 = 0.627. The relative proportion of TCD-dimethanol to dimerdiol thus corresponded to 1.32 to 0.627. The integral of the range from 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 an adjusted integral of 4.80 for TCD-dimethanol and 2.28 for dimerdiol.

[0178] S: 11.77

[0179] Furthermore, the composition of Example 16 according to the invention based on a polymer of isosorbide, tricyclodecanedimethanol and dimer fatty acid can also be calculated from the H-NMR spectrum.

[0180] For the isosorbide content, the signals between 5.3 and 4.5 ppm were used. The integral was set to "40" and corresponds to 4 protons of isosorbide.

[0181] The tricyclodecanedimethanol content was determined from the signals between 4.2 and 3.8 ppm. This range contains four protons of isosorbide and two -CH2- groups of tricyclodecanedimethanol (-O-CH2-). Thus, four protons of tricyclodecanedimethanol are also present in this range.

[0182] The dimer fatty acid content was calculated by integrating the signals at 0.95 - 0.6 ppm.

[0183] Here, two CH3 groups of the dimer fatty acid and one proton of tricyclodecane dimethanol are present. 4 protons of tricyclodecane dimethanol 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 tricyclodecane dimethanol. 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.

[0184] S: 11,704

[0185] Production of the reactants:

[0186] Production of dimer fatty acid diphenyl ester

[0187] 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-neck flask with 0.0025 g (100 ppm) of 4-dimethylaminopyridine. The mixture was inertized by evacuating and venting with nitrogen four times. The mixture was heated to 160 °C using a metal bath. Carbon dioxide evolved at approximately 140 °C. As soon as the flow rate decreased, the temperature was increased to a maximum of 240 °C. Phenol was distilled off. As soon as gas evolution ceased, a vacuum was applied and the pressure was gradually reduced to approximately 1 mbar. The reaction was continued until no more phenol evolved.

[0188] Production of tetrabutylphosphonium acetate

[0189] 483.38 g of an aqueous tetrabutylphosphonum hydroxide solution (mass fraction: 40%) were placed in an Erlenmeyer flask. Approximately 40 mL (0.7 mol) of pure acetic acid were then 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, zeolite (4A) for drying, and 0.5 g of activated carbon for purification were added, and the mixture was allowed to stand for at least 12 hours in a sealed vessel. The product was then filtered and concentrated to maximum at 80 °C and <0.2 mbar. Upon cooling in the gas-tight vessel, the product crystallized at approximately 40 °C. Color: light brown. Preparation of 1,4-cyclohexanedicarboxylic acid diphenyl ester.

[0190] 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-neck flask fitted with a distillation head. The mixture was evacuated four times and inerted with N2 to minimize the oxygen content.

[0191] After melting at 180 °C, CO2 evolved. 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 had ceased (color change), the pressure was reduced to approximately 50 mbar while distilling. N2 was vented and the receiver was changed. The pressure was then reduced further. The intermediate fraction was DPC and could also be removed. The third fraction (<5 mbar, 240 °C) was the main product. Distillation was continued until the bottoms were concentrated to approximately 50 mL, and the white product was removed after cooling. A slight phenol odor was detectable.

[0192] Recrystallization was performed using a hexane / ethyl acetate mixture (approximately 2:1 ratio) and 2-5% of the total mass of activated carbon. The vacuum-filtered product was finely crystalline and bright white.

[0193] Production of diphenyl terephthalate

[0194] 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 1L three-neck flask fitted with a distillation head. The mixture was evacuated four times and inerted with N2 to minimize the oxygen content.

[0195] After heating the suspension to 180 °C, CO2 evolved. As soon as the flow rate decreased, the temperature was increased to a maximum of 260 °C (phenol distills from approximately 220 °C). After gas evolution had ceased (the now clear solution changed color to orange), the pressure was reduced to approximately 50 mbar while distillation was in progress. N2 was added, and the receiver was changed. The pressure was then further reduced. The intermediate run was DPC and could also be removed. As soon as no more distillate formed, the bottoms were poured out.

[0196] After cooling, the product was mechanically ground as finely as possible and boiled with acetone under reflux (the time 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 with suction. The intensely yellow mother liquor was discarded, and the pure, finely crystalline product was dried. The product had a pearlescent luster and a whitish, slightly yellowish color.

[0197] Example 1 (Comparison; PCI)

[0198] Example 2: Polyester carbonate made from 67% isosorbide and 33% CHDA (comparison)

[0199] 51.6 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 of 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 freed of oxygen by evacuating and venting with nitrogen four times. 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 a period of approximately 90 minutes, depending on the observed reactivity. Phenol began to separate. The pressure was then gradually reduced to 0.5 mbar over a period of approximately 30 minutes. Stirring was continued for another 10 minutes at this pressure.

[0200] A transparent, slightly orange-colored polymer with an eta rel of 1.293 was obtained.

[0201] Example 3: Polyester carbonate from cyclohexanedicarboxylic acid, terephthalic acid, dimer fatty acid and isosorbide (comparison)

[0202] 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 fitted with a short-path separator. 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 freed of oxygen by evacuating and venting with nitrogen four times. The mixture was then melted and heated to 160 °C. Carbon dioxide evolution was observed. The temperature was gradually increased to 225 °C over a period of 60 minutes. The pressure was then carefully reduced to 0.5 mbar in several steps over a period of 60 minutes. The temperature was then increased to 235 °C. Stirring was continued for 10 minutes at 235 °C and 0.5 mbar. A yellow polymer with an eta rel of 1.335 was obtained. Example 4: Preparation of a copolycarbonate with dimerdiol without TCD (comparison)

[0203] 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 fitted with a short-path separator. 0.0001 g of sodium ethylhexanoate in the form of 200 μl of an MTBE solution (0.5 g / L) and 0.00389 g (38.9 μl) of tetrabutylphosphonium acetate in an MEK solution (100 g / L) were added to this mixture. The mixture was freed of oxygen by evacuating four times and inerting with nitrogen. The mixture was heated to 160 °C at atmospheric pressure with stirring and melted. Once a homogeneous, low-viscosity liquid was obtained, the temperature was slowly increased to 245 °C with rapid stirring (approx. 500 rpm). Phenol distilled off at approximately 220 °C. The pressure was then carefully reduced step by step to approximately 0.5 mbar, with phenol continuously removed. Stirring was continued at approximately 0.5 mbar for a further 10 minutes at low speed. A transparent, slightly yellow polymer with an eta rel.of 1,389.

[0204] Example 5: Preparation of a copolycarbonate with dimerdiol without TCD (comparison)

[0205] The example was carried out as in Example 4, except that 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 an eta rel of 1.329 was obtained.

[0206] Example 6: Preparation of a copolycarbonate with dimerdiol without TCD (comparison)

[0207] The example was carried out as in Example 4, except that 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 an eta rel of 1.382 was obtained.

[0208] Example 7: Polycarbonate from isosorbide and BEPD (comparison)

[0209] 29.83 g (0.204 mol) of isosorbide, 64.3 g (0.3 mol) of diphenyl carbonate, and 20 ppm of lithium in the form of 75 μl of LiOH solution (100 g LiOH / L) were placed in a flask fitted with a short-path separator. The contents of the flask were freed of oxygen by evacuating four times 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 a period of 30 minutes. Phenol began to separate. The pressure was carefully reduced to 0.5 mbar over a period of 45 minutes. The temperature was then increased to 235 °C. The mixture was stirred at this temperature and pressure for a further 10 minutes. A transparent polymer with an eta rel. of 1.202. Example 8: Polyester carbonate with a low CHDA content (comparison)

[0210] 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 dimer fatty acid diphenyl ester were placed in a flask fitted with a short-path separator and dropping funnel. 0.0015 g (15 μl) of lithium hydroxide in the form of an aqueous solution (100 g / l) was added. The mixture was freed of oxygen by evacuating four times and purging 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 vented to ambient pressure with nitrogen, 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 the addition was complete, phenol distilled off.The temperature was increased to 235 °C and the pressure was carefully reduced stepwise to <1 mbar, continuously removing phenol. Stirring was continued at approximately 0.5 mbar for a further 10 minutes at low speed. A transparent, yellowish polymer with a solution viscosity of 1.27 was obtained.

[0211] Example 9 (Comparison; Polyestercarbonate with CHDA and TCD)

[0212] 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 fitted with a short-path separator and dropping funnel. 0.0015 g (15 μl) of lithium hydroxide in the form of an aqueous solution (100 g / l) was added. The mixture was freed of oxygen by evacuating four times 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 vented to ambient pressure with nitrogen, 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 the addition was complete, phenol distilled off.The temperature was increased to 235 °C and the pressure was carefully reduced stepwise to <1 mbar, continuously removing phenol. Stirring was continued at approximately 0.5 mbar for a further 10 minutes at low speed. A transparent, yellowish polymer with a solution viscosity of 1.27 was obtained. Example 10 (Comparison).

[0213] 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 fitted with a short-path separator. 0.0001 g of sodium ethylhexanoate in the form of 200 μl of an MTBE solution (0.5 g / L) and 0.00389 g (38.9 μl) of tetrabutylphosphonium acetate in an MEK solution (100 g / L) were added to this mixture. The mixture was freed of oxygen by evacuating four times and inerting with nitrogen. The mixture was heated to 160 °C at atmospheric pressure with stirring and melted. Once a homogeneous, low-viscosity liquid was obtained, the temperature was slowly increased to 245 °C with rapid stirring (approx. 500 rpm). Phenol distilled 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. Stirring was continued at approximately 0.5 mbar for a further 10 minutes at low speed.A slightly cloudy, yellow-colored polymer with an eta rel. of 1.294 was obtained.

[0214] Example 11 (Comparison)

[0215] 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 fitted with a short-path separator. 0.0001 g of sodium ethylhexanoate in the form of 200 μl of an MTBE solution (0.5 g / L) and 0.00389 g (38.9 μl) of tetrabutylphosphonium acetate in an MEK solution (100 g / L) were added to this mixture. The mixture was freed of oxygen by evacuating four times and inerting with nitrogen. The mixture was heated to 160 °C at atmospheric pressure with stirring and melted. Once a homogeneous, low-viscosity liquid was obtained, the temperature was slowly increased to 245 °C while stirring rapidly (approx. 500 rpm). Phenol distilled 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. At approximatelyThe mixture was stirred at low speed for 10 minutes at a pressure of 0.5 mbar. A transparent, yellow-colored polymer with an eta rel. of 1.191 was obtained.

[0216] Example 12 (Comparison)

[0217] 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 fitted with a short-path separator. 0.0001 g of sodium ethylhexanoate in the form of 200 μl of an MTBE solution (0.5 g / L) and 0.00389 g (38.9 μl) of tetrabutylphosphonium acetate in an MEK solution (100 g / L) were added to this mixture. The mixture was freed of oxygen by evacuating four times and inerting with nitrogen. The mixture was heated to 160 °C at atmospheric pressure with stirring and melted. Once a homogeneous, low-viscosity liquid was obtained, the temperature was slowly increased to 245 °C while stirring rapidly (approx. 500 rpm). Phenol distilled 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. At approximatelyThe mixture was stirred at low speed for 10 minutes at a pressure of 0.5 mbar. A cloudy, brown polymer with an eta rel. of 1.076 was obtained.

[0218] Example 13 (Comparison)

[0219] 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 fitted with a short-path separator. To this mixture were added 0.0001 g of sodium ethylhexanoate in the form of 200 μl of an MTBE solution (0.5 g / L), 0.00389 g (38.9 μl) of tetrabutylphosphonium acetate in an MEK solution (100 g / L), and 0.0243 g (200 ppm) of DMAP. The mixture was freed of oxygen by four evacuations and inerting with nitrogen, and then heated to 160 °C at atmospheric pressure with stirring and 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 phenol distilled from approximately 220 °C. Once gas evolution had ceased, the pressure was carefully and gradually increased to approximately 245 °C.The mixture was reduced to 0.5 mbar and the temperature was increased to 255 °C. Phenol was continuously removed. Stirring was continued at low speed for 10 minutes at approximately 0.5 mbar. A slightly cloudy, light brown polymer with an eta rel. of 1.338 was obtained.

[0220] Example 14 (Comparison)

[0221] 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 fitted with a short-path separator. 0.0001 g of sodium ethylhexanoate in the form of 200 μl of an MTBE solution (0.5 g / L) and 0.00389 g (38.9 μl) of tetrabutylphosphonium acetate in an MEK solution (100 g / L) were added to this mixture. The mixture was freed of oxygen by evacuating four times and inerting with nitrogen. The mixture was heated to 160 °C at atmospheric pressure with stirring and melted. Once a homogeneous, low-viscosity liquid was obtained, the temperature was slowly increased to 245 °C while stirring rapidly (approx. 500 rpm). Phenol distilled 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. At approximatelyThe mixture was stirred at low speed for 10 minutes at a pressure of 0.5 mbar. A transparent, light yellow polymer with an eta rel. of 1.423 was obtained.

[0222] Example 15 (Comparison)

[0223] 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 fitted with a short-path separator. 0.0001 g of sodium ethylhexanoate in the form of 200 μl of an MTBE solution (0.5 g / L) and 0.00389 g (38.9 μl) of tetrabutylphosphonium acetate in an MEK solution (100 g / L) were added to this mixture. The mixture was freed of oxygen by four evacuations and purging with nitrogen. The mixture was heated to 160 °C at atmospheric pressure with stirring and melted. Once a homogeneous, low-viscosity liquid was obtained, the temperature was slowly increased to 245 °C while stirring rapidly (approx. 500 rpm). Phenol distilled 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. At approximatelyThe mixture was stirred at low speed for 10 minutes at a pressure of 0.5 mbar. A slightly cloudy, light yellow polymer with an eta rel. of 1.339 was obtained.

[0224] Example 16: Preparation of a polyester carbonate containing dimer fatty acid

[0225] (according to the invention)

[0226] 29.22 g (0.0405 mol) of diphenyl ester dimer fatty acid, 17.7 g (0.09 mol) of tricyclodecanedimethanol, 0.0003 g (943.5 ppb) of sodium 2-ethylhexanoate in the form of a solution (5 g / L in MTBE), and 0.0115 g (36 ppm) of tetrabutylphosphonium acetate in the form of a solution (100 g / L in MEK) were placed in a flask equipped with a short-path separator and a dropping funnel. The mixture was freed of oxygen by evacuating four times and purging 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 reaction mixture was then vented to ambient pressure with nitrogen, 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 the addition was complete, phenol distilled off.The temperature was increased to 235 °C and the pressure was carefully reduced stepwise to <1 mbar, continuously removing phenol. Stirring was continued at approximately 0.5 mbar for a further 10 minutes at low speed. A light yellow polymer with an eta rel of 1.240 was obtained.

[0227] Example 17: Preparation of a copolycarbonate with dimerdiol (according to the invention)

[0228] 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 tricyclodecane dimethanol, and 111.8 g (0.765 mol) of isosorbide were placed in a flask fitted with a short-path separator. 0.001 g of sodium ethylhexanoate in the form of 600 μl of an MTBE solution (0.5 g / L) and 116.5 μl of tetrabutylphosphonium acetate in an MEK solution (100 g / L) were added to this mixture. The mixture was freed of oxygen by evacuating four times and purging with nitrogen, melted, and heated to 160 °C at atmospheric pressure with stirring. 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 at approximately 220 °C. The pressure was then carefully reduced gradually to approximately 0.5 mbar, continuously removing phenol. Stirring was continued at approximately 0.5 mbar for another 10 minutes at low speed.A light-colored, transparent polymer with an eta rel. of 1.356 was obtained.

[0229] Example 18: Preparation of a copolycarbonate with dimerdiol (according to the invention)

[0230] The example was carried out as in Example 17, except that 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 an eta rel of 1.320 was obtained.

[0231] Example 19: Preparation of a copolycarbonate with dimerdiol (according to the invention)

[0232] The example 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 light yellow polymer with an eta rel of 1.325 was obtained. Example 20: Preparation of a Copolycarbonate with Dimerdiol (According to the Invention)

[0233] The example was carried out as in Example 17, except that 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 an eta rel of 1.352 was obtained.

[0234] Example 21: Preparation of a copolycarbonate with dimerdiol (according to the invention)

[0235] The example was carried out as in Example 17, except that 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 light yellow polymer with an eta rel of 1.331 was obtained.

[0236] Example 22: Preparation of a copolyestercarbonate containing dimer fatty acid and terephthalic acid (according to the invention)

[0237] 64.23 g (0.300 mol) of diphenyl carbonate, 4.95 g (0.0253 mol) of tricyclodecane dimethanol, 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 fitted with a short-path separator. 0.00571 g of tetrabutylphosphonium acetate and 0.0114 g of DMAP were added to this mixture. The mixture was freed of oxygen by evacuating four times and inerting with nitrogen. The mixture was heated to 160 °C at atmospheric pressure with stirring and melted. Once a homogeneous, low-viscosity liquid was obtained, the temperature was slowly increased to 245 °C with rapid stirring (approx. 500 rpm). Carbon dioxide evolution was observed, and phenol distilled off at approximately 220 °C. After the gas evolution had ceased, the pressure was carefully and gradually reduced to approximately 0.5 mbar, while the temperature was increased to 255 °C. Phenol was continuously removed. At approximatelyThe mixture was stirred at low speed for 10 minutes at a pressure of 0.5 mbar. A transparent, reddish polymer with an eta rel. of 1.206 was obtained. Table 1: Hot water resistance.

[0238] Table 2: Further durability tests

[0239] Table 3: Shear rheology hot water. Surprisingly, polymers made from frequently used diols such as cyclohexanedimethanol and isosorbide (Example 1) - as described, for example, in EP 2033981 - are not very stable when exposed to hot water. Other diols, such as the combination of sterically hindered diols such as isosorbide and 2-butyl-2-ethyl-1,3-propanediol, also do not display good stability (Example 7). This is surprising because 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 isosorbide also do not display good stability in the hot water test. This was surprising because polyesters made from cyclohexanedimethanol and 1,4-cyclohexanedicarboxylic acid, for example, display high stability against aqueous media.

[0240] Example 11 shows that the combination of isosorbide and long-chain diols—in this case, dodecanediol (cf. EP2840102)—does not necessarily lead to better results. 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.

[0241] It is known that aromatic polyesters are often stable against hot water exposure. 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 consisting of aliphatic building blocks surprisingly does not lead to stable products, as shown in Example 3. The incorporation of dimer fatty acids into such structures does not help either. It would have been expected that the nonpolar or hydrophobic properties of the aromatic acids or dimer fatty acids would improve stability against water. Surprisingly, this also applies in part to polymers containing TCD alcohol. For example, a polymer composed of isosorbide, cyclohexanedicarboxylic acid, dimer fatty acid, and TCD dimethanol is surprisingly unstable (Example 8). This can be attributed to the presence of cyclohexanedicarboxylic acid.

[0242] Surprisingly, polymers that essentially consist only of isosorbide and long-chain non-polar fatty acids such as sebacic acid are also not stable against hot water (Example 13).

[0243] The combination of dimer diol or dimer fatty acid and isosorbide demonstrates high resistance to aqueous media. Surprisingly, however, these polymers exhibit a high melt viscosity (Examples 4 to 6). Rheological studies demonstrate that the viscosity is significantly higher than that of the polymers of the invention. The high melt viscosity is a critical disadvantage because it significantly complicates the processing of these materials. A significant increase in process temperatures to increase flowability is not possible with aliphatic materials because 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 ISB and dimer diol (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 inventive copoly(ester)carbonates 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), while simultaneously demonstrating high surface hardness with sufficiently good mechanical properties.

[0244] It can also be seen that the polymers according to the invention have glass transition temperatures of more than 110 °C.

[0245] Table 4: Scratch resistance

[0246] The results in Table 4 show that with increasing Pripol content and in the absence of TCD-dimethanol, scratch resistance decreases (although Tg and molecular weight do not vary significantly between experiments). In contrast, the inventive copolymers with lower Tg but with TCD-dimethanol as a comonomer exhibit better scratch resistance.

[0247] Table 5: Charpy impact test

[0248] Table 6: 'H-NMR spectroscopy

[0249] 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 completely present in the copoly(ester)carbonate. This means that the ratio and amount of the structural units present in the resulting polymer can be controlled by the ratio and amount of the input materials.

Claims

Patent claims:

1. Copoly(ester)carbonate containing the units (A), (B), (C), optionally (D) and optionally units different from (A), (B), (C) and (D), with where each r and each s independently represents a number between 0 and 4, and each R 1 independently represents a structure of the formulas (RIA), (RIB), (R1C) or (R1D) (R1B), where b is 0 or 1, marked positions in formulas (RIA) to (RID) are the positions where the (CFfijr group or (CFEjs group) shown in formula (B) is located, and where both t are independent of R 2 are either 0 or 1 at the same time and each R 2 independently of one another represents an aliphatic group having 16 to 44 carbon atoms, which may contain one or more double bonds, wherein at least partially direct links are present between the units (A), (B), (C), optionally (D) and optionally units different from (A), (B), (C) and (D), wherein, if there is a direct link between at least two of the units selected from the group consisting of (A), (B), (C) and optionally (D), the position of the units (A), (B), (C), (D) marked with marked position of these units, with the exception that when t in formula (C) is 0, there is no direct linkage between two units (C) with each other, when t in formula (C) is 0, there is no direct linkage between unit (C) and unit (D) and there is no direct linkage between two units (D) with each other, wherein the copoly(ester)carbonate comprises 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% data refer to the total amount of units (A), (B), (C), if appropriate (D) and, where appropriate, units different from (A), (B), (C) and (D).

2. Copoly(ester)carbonate according to claim 1, characterized in that unit (A) is represented by formula (A*) with where n is the average number of repeating units, and / or that unit (B) is represented by formula (B*) with where m represents the mean number of repeat units.

3. Copoly(ester)carbonate according to one of claims 1 or 2, characterized in that r and s in the formulas (B) and (B*) are 1 and R 1 in formulas (B) and (B*) represents the structure of formula (RIA).

4. Copoly(ester)carbonate according to one of claims 1 to 3, characterized in that R 2in formula (C) is represented by the following formula (R2A) with CH3 R 11 _ R11 — Y — R 11 - - R" 0Hs (R2A), wherein Y represents a bridging structure selected from the group consisting of an alkylene group having 1 to 4 carbon atoms, an alkylidene group having 1 to 4 carbon atoms and a cycloalkylene group having 4 to 12 carbon atoms, wherein the cycloalkylene group optionally contains one or more double bonds and / or is optionally condensed to one or more further cycloalkylene groups, wherein the one or more further cycloalkylene groups optionally each have one or more double bonds, wherein the R adjacent to the bridging structure 11 -groups are bound to any position of the bridging structure and where each R 11independently of one another represents an alkylene group having 1 to 12 carbon atoms or an alkylidene group having 1 to 12 carbon atoms, with the proviso that the structure of formula (R2A) comprises 16 to 44 carbon atoms and wherein the positions marked with , in formula (R2A) are the positions at which the (O)t groups shown in formula (C) are located.

5. Copoly(ester)carbonate according to claim 4, characterized in that the formula (R2A) is represented by one of the formulas (R2Aa), (R2Ab), (R2Ac) or (R2Ad), with where each R 11 and each has the meanings given in claim 4, the cycle of Formula (R2Ac) optionally contains one or two double bonds and each cycle of formula (R2Ad) independently optionally contains one or two double bonds.

6. Copoly(ester)carbonate according to claim 4 or 5, characterized in that each R 11independently represent an alkylene group having 1 to 10 carbon atoms, with the proviso that the structure of formula (R2A) comprises 16 to 44 carbon atoms.

7. Copoly(ester)carbonate according to one of claims 1 to 6, characterized in that the group represented by R 2 , (R2A), (R2Aa), (R2Ab), (R2Ac) and / or (R2Ad) has 21 to 44 carbon atoms in the unit (C).

8. Copoly(ester)carbonate according to one of claims 1 to 7, characterized in that the copoly(ester)carbonate consists of at least 80% by weight of the units (A), (B), (C) and optionally (D).

9. Copoly(ester)carbonate according to one of claims 1 to 8, characterized in that the copoly(ester)carbonate has direct links between the units (A) and (C) and both t in unit (C) are simultaneously 0.

10. Copoly(ester)carbonate according to one of claims 1 to 9, characterized in that the copoly(ester)carbonate is at least 50 mol% bio-based.

11. Copoly(ester)carbonate according to one of claims 1 to 10, characterized in that the copoly(ester)carbonate 5 to 20 mol% of unit (B), 3 to 12 mol% of unit (C) and at least 65 mol% of unit (A), wherein the mol% data relate to the total amount of units (A), (B), (C), optionally (D) and optionally units different from (A), (B), (C) and (D).

12. Copoly(ester)carbonate according to claim 12, characterized in that the copoly(ester)carbonate 8 to 12 mol% of unit (B), 3.5 to 8.0 mol% of unit (C) and at least 80 mol% of unit (A), wherein the mol% data relate to the total amount of units (A), (B), (C), optionally (D) and optionally units different from (A), (B), (C) and (D).

13. Composition containing the copoly(ester)carbonate according to any one of claims 1 to 12 and one or more additives.

14. A molded part containing the copoly(ester)carbonate according to any one of claims 1 to 12 or containing the composition according to claim 13.

15. A process for the preparation of the copoly(ester)carbonate according to any one of claims 1 to 12, comprising at least the reaction of a 1,4:3,6-dianhydrohexitol, a diol of formula (B2), at least one further compound selected from the group consisting of a diol of formula (C2), a compound of formula (C3) or any mixtures thereof and a carbonyl source, wherein HO - (CH2) r — R1 — (CH2) S - OH (B2), where each r and each s independently represents a number between 0 and 4 and each R 1 independently represents a structure of the formulas (RIA), (R1B), (R1C) and (R1D) where b is 0 or 1, w , g in formulas (RIA) to (R1D) are the positions where the (CH2) shown in formula (B2) r -group or (CH2) S -group, and HO - R 2 — -OH (C2), (C3), where each R 2 in formulas (C2) and (C3) independently of one another represents an aliphatic group having 16 to 44 carbon atoms, which may contain one or more double bonds, and each R 3 in the formula (C3) independently of one another represent hydrogen, chlorine or -OR", where R" represents an aliphatic or aromatic radical.

Images