Process for producing an amorphous polyestercarbonate by direct esterification

Abstract

The present invention relates to an ecologically and economically advantageous process for producing an amorphous polyestercarbonate comprising structures derived from a 1,4:3,6-dianhydrohexitol and / or tricyclodecanedimethanol, to a polyestercarbonate likewise comprising said structures, to a molding composition comprising a polyestercarbonate, and to a molded article comprising a polyestercarbonate.

Description

[0001] 2025PF30027- Abroad

[0002] - 1 - METHOD FOR THE PRODUCTION OF AN AMORPHEN POLYESTER CARBONATE BY DIRECT ESTIFICATION

[0003] The present invention relates to a process for producing an amorphous polyester carbonate comprising structures derived from 1,4:3,6-dianhydrohexitol and / or tricyclodecanedimethanol, a polyester carbonate also comprising said structures, a molding compound comprising a polyester carbonate, and a molded body comprising a polyester carbonate. It is known that polyesters, polycarbonates, and polyester carbonates exhibit good mechanical properties, heat resistance, and weather resistance. Each polymer group exhibits certain key characteristics, depending on the monomers used, that distinguish such materials. For example, polycarbonates exhibit particularly good mechanical properties, whereas polyesters often show better chemical resistance. Depending on the monomers selected, polyester carbonates exhibit property profiles from both of these groups.

[0004] Aromatic polycarbonates and polyesters, in particular, exhibit weaknesses in terms of aging and weathering resistance. For example, absorption of UV light leads to yellowing and potentially embrittlement of these thermoplastic materials. Aliphatic polycarbonates and polyester carbonates offer better properties in this regard, especially improved aging and / or weathering resistance, as well as superior optical properties (such as better transmission). At the same time, established processes exist for processing aromatic polycarbonates and polyesters. These include injection molding, (co)extrusion, blow molding, and thermoforming.

[0005] The disadvantage of aliphatic polycarbonates or polyester carbonates is often their low glass transition temperature. This low glass transition temperature limits their application possibilities and means that aliphatic polycarbonates or polyester carbonates often cannot be considered a full replacement for classic aromatic polycarbonates or polyester carbonates. Furthermore, processes for the production of aliphatic polycarbonates, polyesters, and polyester carbonates present different challenges than corresponding processes using aromatic starting materials or products. For example, polyesters from 1,4-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid are produced starting from the dimethyl ester of the diacid. However, phenyl esters are significantly more reactive than their aliphatic analogs in the transesterification reaction. Processes for the production of polyester carbonates using phenyl esters as an intermediate step are described in EP 3026074 Al and EP 3248999 Al.

[0006] - 2 - The production of these phenyl esters, however, starts with the corresponding acid chlorides. These, in turn, are produced using phosgene. The phosgene process additionally requires the use of solvents—mostly halogenated solvents—which must be recycled or disposed of in a complex process. Therefore, it is advantageous to provide a phosgene-free process that ideally requires no solvents at all.

[0007] Kricheldorf et al. describe the synthesis of polyesters from isosorbide and cyclohexanedicarboxylic acid in Macromol. Chem. Phys. 2010, 211, 1206-1214. To obtain the desired molar masses, they used the two components in equimolar amounts. However, under these conditions, they were unable to obtain a polymer from the reaction of isosorbide with free cyclohexanedicarboxylic acid. Activation of the acid using an acid chloride was necessary to achieve a higher molecular weight. Similarly, the use of a dimethyl ester did not work well.

[0008] EP 0684270 A2 describes the production of aliphatic polyester carbonates. This document focuses primarily on the use of bemotic acid and butanediol. The aim is to provide a biodegradable polyester carbonate with a melting point of 70–180 °C. Therefore, this document concerns crystalline polyester carbonates. In a first step, bemotic acid is esterified with butanediol, removing the resulting water and excess butanediol. This results in an increased molecular weight of the oligoester, which is sufficiently high to achieve the specified melting points of the final polyester carbonate while remaining low enough to ensure good biodegradability. However, due to shrinkage, crystalline polyester carbonates are not particularly suitable for processing using the plasticizing methods commonly used for aromatic polycarbonates.

[0009] EP 0 823 449 A2 aims to improve the thermal properties, such as the melt stability, of the polyester carbonates mentioned in EP 0 684 270 A2. To this end, it essentially proposes the incorporation of branched structures into the polyester carbonate chain. The polyester carbonates disclosed therein are also crystalline.

[0010] EP 0 131 164 Al describes the production of polyester carbonates based on non-aromatic dicarboxylic acids and non-aromatic diols. The process is reversibly stopped upon reaching a desired degree of condensation and then continued. The production of the oligoesters used to form the polyester carbonate is not described. The polyester carbonates produced there are rubber-like, flowable at room temperature, and therefore exhibit very low glass transition temperatures. Consequently, they cannot be processed using the plasticizing methods commonly used for aromatic polycarbonate. 2025PF30027- Abroad

[0011] - 3 - It is also known that polymer properties can be influenced by the targeted incorporation of comonomers (see also the incorporation of trifunctional monomers in EP 0 823 449 A2 described above). For example, the as-yet-unpublished PCT / EP2024 / 076755 optimizes properties such as chemical resistance of isosorbide-based polyester carbonates by incorporating specific comonomers. These polyester carbonates are based, among other things, on cycloaliphatic diols. Furthermore, these polyester carbonates are linear. The process described therein is either a one-pot process in which at least a portion of the acid reacts with diphenyl carbonate, or a process in which at least two equivalents of diphenyl carbonate are reacted with one equivalent of the dicarboxylic acid to form the diphenyl ester. This reaction releases two equivalents of carbon dioxide and two equivalents of phenol.The dicarboxylic acid, activated as a diester, then incorporates into the polyester carbonate. However, the described process can be improved from both ecological and economic perspectives. In particular, the carbon balance of the polyester carbonate production process can be optimized due to the release of carbon dioxide. Furthermore, the relatively large reactor volume required due to the release of phenol can also be optimized.

[0012] Based on the prior art, the objective was therefore to overcome at least one, preferably all, disadvantages of the prior art. In particular, the objective of the present invention was to provide a polyester carbonate using (in combination with) aliphatic starting materials, which can be processed using the plasticizing methods commonly used for aromatic polycarbonate (e.g., injection molding, (co)extrusion, blow molding, thermoforming). For this purpose, the polyester carbonate should be amorphous and have a glass transition temperature of at least 90 °C. The use of (in combination with) aliphatic starting materials should enable the polyester carbonate to exhibit good optical properties (especially transparency). In particular, it was important to achieve thermal stability comparable to that of conventional aromatic polycarbonates.The invention was based, in particular, on the objective of providing a process for the production of a polyester carbonate, preferably a polyester carbonate with at least one, and more preferably all, of the aforementioned properties, which is particularly simple and at the same time yields a polyester carbonate of high quality and good properties. The process should be as ecologically and economically viable as possible. This preferably means that the process comprises as few process steps as possible. In particular, this means that the process has a favorable carbon balance. Specifically, a process should be provided that does not require solvents and / or the use of difficult-to-handle substances such as phosgene. 2025PF30027- Abroad.

[0013] - 4 - At least one, and preferably all, of the aforementioned problems were solved by the present invention. Surprisingly, it was found that a polyester carbonate exhibiting the desired properties could be obtained through a defined process sequence. For this purpose, 1,4:3,6-dianhydrohexitol and / or tricyclodecanedimethanol were first esterified with a dicarboxylic acid. The resulting compound (A) with at least two ester groups has a low acid number. This means that the resulting compound is essentially OH-terminated. Subsequently, this compound is reacted with a diaryl carbonate and / or dialkyl carbonate to form a polyester carbonate. It was extremely surprising that the previously formed compound (A) with at least two ester groups was effectively incorporated into the polyester carbonate and that sufficiently high molecular weights could be achieved.A "sufficiently high molecular weight" is preferably understood as a polymer with a relative solution viscosity above 1.20, particularly preferably from 1.21 to 1.65, further preferably from 1.22 to 1.63, particularly preferably from 1.23 to 1.62, and most preferably from 1.26 to 1.55. The targeted selection of a 1,4:3,6-dianhydrohexitol and / or tricyclodecanedimethanol as the diol leads to polyester carbonates exhibiting a glass transition temperature of at least 90 °C. At the same time, these two diols are challenging to incorporate into polyester carbonates. In particular, 1,4:3,6-dianhydrohexitols such as isosorbide possess differently reactive OH groups. Therefore, it is not always possible to selectively incorporate these diols into a polymer. It is also known that excessively high temperatures can decompose 1,4:3,6-dianhydrohexitols such as isosorbide.The lack of reactivity of this compound often cannot be compensated for simply by increasing reaction temperatures. In particular, the present invention offers the advantage of enabling targeted construction of the polymer structure. It is highly beneficial to react specific monomers first, regardless of their reactivity, and incorporate them as pre-reacted products (compound (A) with at least two ester groups) into the polyester carbonate. This allows for better control of the polymer architecture, which can lead to targeted improvements in properties. For example, the specific diols 1,4:3,6-dianhydrohexitol and / or tricyclodecanedimethanol can be reacted first in the process step (i) according to the invention to protect them from thermal influences and oxidation. Furthermore, the process according to the invention makes it possible to bridge only certain monomers via ester groups, while other monomers may be bridged separately.The esters are preferably bridged via carbonate units. This can also be advantageous for the property profile of the resulting polyester carbonate. For example, if certain ester groups are susceptible to hydrolysis, it makes sense to limit the proportion of these ester groups in the resulting polyester carbonate. That is, it is advantageous to be able to control the polymer architecture during the process according to the invention. In addition, the reaction progress of process step (i) is particularly easy to monitor by determining the acid number. 2025PF30027- Abroad.

[0014] - 5 - This is not the case, for example, if a dimethyl ester is used instead of the free acid. Furthermore, the use of the free acid produces water, which can be easily removed from the reaction and also has no negative impact on the subsequent process step (ii) (as methanol would, for example). According to the invention, it has been found that by achieving the low acid number in process step (i), the carbon balance can be significantly improved compared to the prior art. In the process step (i) according to the invention, water is produced. This can be easily separated from compound (A) and requires no additional safety precautions. In the prior art, for example, a diphenyl ester is activated by the reaction of the dicarboxylic acid with two equivalents of diphenyl carbonate. This releases carbon dioxide.The previously bound carbon is thus "lost," resulting in a disadvantageous carbon balance in the prior art. The invented process is therefore both ecologically and economically advantageous. It requires no solvents. Furthermore, no difficult-to-handle substances, such as phosgene, are needed. Overall, it offers a high degree of flexibility to selectively synthesize and maintain polyester carbonates, even with challenging structural units, under simultaneously very favorable ecological conditions. This process yields polyester carbonates that can be processed using the plasticizing methods commonly used for aromatic polycarbonates (e.g., injection molding, (co)extrusion, blow molding, thermoforming). They are amorphous and exhibit a glass transition temperature of at least 90 °C. The polyester carbonates produced according to the invention offer the advantage of having properties similar to those of conventional aromatic polycarbonates.Because the polyester carbonates according to the invention are amorphous, they exhibit no shrinkage. The term "shrinkage" is familiar to those skilled in the art in the field of polymers, particularly crystalline polymers. Preferably, the term refers to the effect that, upon cooling of a polymer melt, the formation of crystals leads to a reduction in volume. This results in a decrease in the volume and dimensions of an injection-molded part compared to the original shape. This can be avoided by using an amorphous polymer. While crystalline polymers can be used in extrusion or injection molding processes, shrinkage must always be taken into account for the resulting molded part. Therefore, aromatic polycarbonates cannot simply be replaced by crystalline polymers in standard plasticizing processes.Furthermore, the polyester carbonates according to the invention are linear, which allows their structure to be precisely and selectively controlled in the inventive process. Due to the (co-)use of aliphatic starting materials, the polyester carbonate according to the invention has good optical properties (especially transparency). In addition, thermal stability comparable to that of conventional aromatic polycarbonates has been achieved. Preferably, the polyester carbonate according to the invention is thermoplastic. According to the invention, it is preferably registered under the name 2025PF30027- Abroad.

[0015] - 6 - The term "thermoplastic" is understood to mean a polymer that can be deformed within a temperature range, particularly above room temperature, and especially above 90 °C. This deformation is preferably reversible. In particular, the term "thermoplastic" is used, according to the invention, preferably to distinguish thermoset and / or elastomeric polymers. Such thermoset and / or elastomeric polymers exhibit physical cross-linking of the individual polymer chains, which results in deformation (exceeding the elastic range) being irreversible. Such polymers cannot be deformed / shaped by conventional plasticizing processes.

[0016] Furthermore, it was found that an additional advantage of the inventive process is the improved utilization of the reactor volume. In process step (i) of the inventive process, water is produced by the reaction of the OH groups with the acid groups. This requires less volume than phenol, which is classically produced in the prior art by the reaction of the acid with diphenyl carbonate. Moreover, the water is easier to separate from the reaction mixture of process step (i) than phenol. Overall, the reactor volume is used more efficiently in the inventive process than in the prior art, which increases the economic viability of the process.

[0017] According to the invention, a process for producing an amorphous polyester carbonate with a glass transition temperature > 90 °C is provided, comprising the steps

[0018] (i) Esterification of a 1,4:3,6-dianhydrohexitol and / or of tricyclodecanedimethanol with at least one dicarboxylic acid and / or an anhydride of a dicarboxylic acid to obtain a compound (A) having at least two ester groups and an acid number of less than 10 mg KOH / g and

[0019] (ii) Reaction of compound (A) with at least one diaryl carbonate and / or dialkyl carbonate to obtain the polyester carbonate.

[0020] The ecological and economic advantages of the inventive process can be ensured by the sequence of at least the process steps (i) and (ii).

[0021] Procedure step (i)

[0022] In process step (i) an esterification takes place. The term "esterification" is known to those skilled in the art. In particular, according to the invention, it is understood to be the reaction of a 1,4:3,6-dianhydrohexitol and / or the tricyclodecanedimethanol with a dicarboxylic acid and / or an anhydride of a dicarboxylic acid with elimination of water. In particular, it is preferred that 2025PF30027- Abroad

[0023] - 7 -that process step (i) is carried out with the removal of the water formed by the esterification. Such removal can be complete, substantially complete, or only partial. The person responsible is aware that the removal of the water can affect the equilibrium of the esterification in process step (i). They can therefore choose the optimal procedure for the respective process. In some cases, the process control of process step (i) can automatically result in the removal of the water, for example, through temperature control and / or the application of a vacuum.

[0024] According to the invention, in process step (i) a 1,4:3,6-dianhydrohexitol and / or tricyclodecanedimethanol are used. Both diols are cycloaliphatic. Thus, they influence the glass transition temperature of the resulting polyester carbonate.

[0025] As is known to experts, 1,4:3,6-dianhydrohexitols are generally selected from the group consisting of isomannide, isoidide, and isosorbide. These can be bio-based compounds, thus offering all the advantages of a bio-based monomer and the resulting polymer (e.g., improved sustainability, as they are accessible from renewable resources). The process according to the invention is particularly preferred in that at least one of the 1,4:3,6-dianhydrohexitols is isosorbide.

[0026] Tricyclodecanadimethanol is also known as TCD alcohol or [8-(hydroxymethyl)-3-tricyclo[5.2.1.02,6]decanyl]methanol. Tricyclodecanadimethanol typically exists as a mixture of isomers. Up to 32 isomers are possible. Depending on the polymerization reaction conditions, the initial number and / or types of isomers of the monomer can also change in the resulting polymer.

[0027] Preferably, the dicarboxylic acid in process step (i) is selected from the group consisting of the compounds represented by formula (1), (2) and (3), sebacic acid, furandicarboxylic acid, naphthalendicarboxylic acid, phthalic acid, isophthalic acid and terephthalic acid or the corresponding anhydrides of the aforementioned acids, wherein

[0028]

[0029] wherein in formulas (1) and (2)2025PF30027- Abroad

[0030] - 8 - B each independently of each other stands for a CfF group or a heteroatom selected from the group consisting of O and S, preferably a CH2 group or an oxygen atom,

[0031] Ri each independently represents a single bond or an alkylene group with 1 to 10 carbon atoms, preferably a single bond or an alkylene group with 1 to 5 carbon atoms, in particular preferably a single bond, and

[0032] n is a number between 0 and 3, preferably 0 or 1, and

[0033] O, ,0

[0034] H° OH (3X

[0035]

[0036] wherein in formula (3) each R 2 Each term represents an aliphatic group with 16 to 44 carbon atoms, which may contain one or more double bonds. It is readily apparent to a person skilled in the art what the anhydrides of the aforementioned dicarboxylic acids look like. Sebacinic anhydride and phthalic anhydride are particularly favored.

[0037] It is preferred that the at least one dicarboxylic acid is an aliphatic dicarboxylic acid. This excludes furandicarboxylic acid, naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, and terephthalic acid from the group described above. Particularly preferably, the at least one dicarboxylic acid is a mixture of at least one aliphatic dicarboxylic acid, preferably selected from the dicarboxylic acids described above, and at least one aromatic dicarboxylic acid, preferably selected from furandicarboxylic acid, naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, and terephthalic acid. The combination of 1,4-cyclohexaneedicarboxylic acid and terephthalic acid is especially preferred. The combination of a dimer fatty acid and terephthalic acid is also particularly preferred.

[0038] With regard to formulas (1) and (2), it is understood that if Ri represents a single bond, then Ri contains zero carbon atoms.

[0039] In particular, it is preferred that the dicarboxylic acid of formula (1) or (2) is selected from the group consisting of 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, tetradihydro-2,5-furandicarboxylic acid, tetradihydro-2,5-dimethyl-furandicarboxylic acid, decahydro-2,4-naphthalenedicarboxylic acid, decahydro-2,5-naphthalenedicarboxylic acid, decahydro-2,6-naphthalenedicarboxylic acid, and decahydro-2,7-naphthalenedicarboxylic acid. [2025PF30027- Abroad]

[0040] - 9 -any mixtures may be used. Most preferred are 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid or 1,2-cyclohexanedicarboxylic acid.

[0041] Any R is especially preferred 2in formula (3) independently for 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.

[0042] In the context of the present invention, the term "aliphatic" or "aliphatic group," unless otherwise defined, refers to a hydrocarbon group that does not contain aromatic units. However, this group may contain one or more double bonds. Furthermore, this group may contain one or more cycles. These cycles may be fused together (i.e., for example, one or more carbon atoms may belong to two cycles) or linked together by, for example, alkylene or alkylidene groups. These one or more cycles may contain one or more double bonds. It should be noted, however, that aromatic cycles are not included in the definition of "aliphatic" according to the invention. In addition, the one or more cycles or the aliphatic group itself may be interrupted by one or more heteroatoms. This, however, is less preferred.

[0043] In the context of the present invention, the term “alkyl” or “alkyl group” preferably refers, unless otherwise specified, to an alkane structure from which one hydrogen atom has been removed. The alkyl group according to the present invention can be linear or branched. It is saturated and therefore comprises only single bonds between the adjacent carbon atoms. The alkyl group preferably includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, neopentyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1,2-Dimethylpropyl, 1-Methylpentyl, 2-Methylpentyl, 3-Methylpentyl, 4-Methylpentyl, 1,1-Dimethylbutyl, 1,2-Dimethylbutyl, 1,3-Dimethylbutyl, 2,2-Dimethylbutyl, 2,3-Dimethylbutyl, 3, 3-Dimethylbutyl, 1-Ethylbutyl, 2-Ethylbutyl, 1,1,2-Trimethylpropyl, 1,2,2-2025PF30027- Foreign

[0044] - 10-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, within the scope of the present invention, the number of carbon atoms is defined differently.

[0045] In the context of the present invention, the term “alkylene” or “alkylene group” preferably refers, unless otherwise specified, to a bridging alkane structure from which two hydrogen atoms have been removed from different carbon atoms. In this context, the two hydrogen atoms removed from the two carbon atoms can be from any carbon atoms in the alkane structure. This means that the two carbon atoms can be adjacent, but need not be. An alkylene group can be linear or branched. It is saturated. If the alkylene group comprises only one carbon atom, it is a methylene group (-CH2-) which is connected to the rest of the molecule via two single bonds.Preferably, the alkylene group comprises methylene, ethylene, n-propylene, 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-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, within the scope of the present invention, the number of carbon atoms is defined differently.Furthermore, according to the present invention, the alkylene group can optionally comprise at least one carbonyl group, optionally at least one halogen atom, and / or optionally be interrupted by at least one heteroatom. Examples of such alkylene groups are -C(=O)-(CH2)4-C(=O)-, -C(=O)-(CH2)3-C(=O)-, -C(=O)-(CH2)2-C(=O)-, -C(CF3)2, -O-(CH2)4-O-, -O-(CH2)3-O-, -O-(CH2)2-O-, and the like. However, the aforementioned structures are less preferred according to the invention. In addition, the invention also refers to a "cycloalkylene group." In this case, the above-mentioned characteristics apply, with the addition that the group can further comprise one or more cycles. These cycles can be condensed together (i.e., for example, one or more carbon atoms can belong to two cycles) or linked together by, for example, alkylene groups. This one or more cycles can contain one or more double bonds.Furthermore, one or more cycles or the aliphatic group itself can be interrupted by one or more heteroatoms. However, this is less preferred. 2025PF30027- Abroad.

[0046] - 11 - In the context of the present invention, the term “alkylidene” or “alkylidene group” preferably refers, unless otherwise specified, to a bridging alkane structure in which two hydrogen atoms have been removed from the same carbon atom. The alkylidene group optionally comprises at least one carbon-carbon double bond, optionally at least one carbonyl group, and / or optionally at least one halogen atom. Preferably, the alkylidene group comprises isopropylidene, n-propylidene, isoheptylidene, and the like.

[0047] In the context of the present invention, the term “aralkyl” preferably refers, and unless otherwise specified, in each case independently, to a linear, cyclic, or branched alkyl group that is singly, doubly, or multiply substituted with aryl groups. In the context of the present invention, the term “aryl” preferably refers, and unless otherwise specified, to an aromatic hydrocarbon group. Examples of “aryl” are phenyl, o-, p-, m-toluyl, naphthyl, phenanthryl, or anthranceryl.

[0048] In the context of the present invention, the term “alkoxy” or “alkoxy group” preferably refers, unless otherwise specified, to a linear, cyclic, or branched alkyl group that is simply bonded (-OR) to an oxygen atom. Preferably, alkoxy groups according to the present invention have 1 to 6 carbon atoms. Particularly preferably, alkoxy groups comprise methoxy, ethoxy, α-propoxy, iso-propoxy, α-butoxy, and β-butoxy.tert-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.

[0049] Based on the definitions mentioned above, the professional is able to understand further definitions that are not explicitly mentioned above.

[0050] According to the invention, it is preferred that R 2in formula (3) is represented by the following formula (R2A) with 2025PF30027- Abroad

[0051] - 12 - CH3

[0052] R 11

[0053] - R 11 — Y— R" - I

[0054] R 11

[0055]

[0056] where Y represents a bridging structure selected from the group consisting of an alkylene group with 1 to 4 carbon atoms, an alkylidene group with 1 to 4 carbon atoms, and a cycloalkylene group with 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms, wherein the cycloalkylene group optionally contains one or more double bonds and / or is optionally fused to one or more further cycloalkylene groups, wherein the one or more further cycloalkylene groups optionally each have one or more double bonds.

[0057] where the R adjacent to the bridging structure 11 -groups are bound to any position of the bridging structure and

[0058] where each R 11 independently of each other stands for an alkylene group with 1 to 12 carbon atoms or an alkylidene group with 1 to 12 carbon atoms, provided that the structure of formula (R2A) comprises 16 to 44 carbon atoms and wherein the positions marked with , in formula (R2A) are the positions where the (C=O) groups shown in formula (3) are located.

[0059] The formula (R2A) is particularly preferred when represented by one of the formulas (R2Aa), (R2Ab), (R2Ac) or (R2Ad), with

[0060] H3C ~ H3C ~

[0061] R 11 R 11 \n R 11

[0062] CH— CH C=C

[0063] R n \ii R 11 \ii

[0064] X ''CHQ CH3

[0065]

[0066] 3 (R2Aa), (R2Ab),2025PF30027- Abroad

[0067]

[0068] where each R 11 and each,

[0069]

[0070] the meanings mentioned for (R2A), the cycle of formula (R2Ac) optionally has one or two double bonds, and each cycle of formula (R2Ad) optionally contains one or two double bonds independently of each other. It is also particularly preferred that R 2 Formula (3) 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 (i.e., two groups that fall under formula (R2Aa)).

[0071] As explained in more detail above, the cycles of the formulas (R2Ac) and / or (R2Ad) can each contain one or two double bonds. This does not usually imply the formation of an aromatic ring. As explained further below, it is possible that if R 2 Formula (3) comprises a mixture of at least two different formulas (R2Aa), (R2Ab), (R2Ac) and (R2Ad), and also contains small amounts of aromatic bridging structures Y according to formula (R2A). However, this is less preferred.

[0072] Any R is especially preferred 11 in formula (R2A) and / or in formulas (R2Aa), (R2Ab), (R2Ac) or (R2Ad) independently for an alkylene group with 1 to 10 carbon atoms, provided that the structure of formula (R2A) and / or in formulas (R2Aa), (R2Ab), (R2Ac) or (R2Ad) comprises 16 to 44 carbon atoms.

[0073] It is also preferred that the R 2, (R2A), (R2Aa), (R2Ab), (R2Ac) and / or (R2Ad) the group described in formula (3) has 21 to 44 carbon atoms. It is equally preferred that the group described by R 2 , (R2A), (R2Aa), (R2Ab), (R2Ac) and / or (R2Ad) described in formula (3) 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 372025PF30027- Abroad

[0074] - 14 - carbon atoms, in particular preferably 29 to 37 carbon atoms, in particular preferably 30 to 37 carbon atoms, in particular preferably 31 to 37 carbon atoms, in particular preferably 32 to 37 carbon atoms and most preferably 33 to 37 carbon atoms. The person skilled in the art is able to apply this limited number of carbon atoms to the above specifications regarding the number of carbon atoms.

[0075] 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.

[0076] Formula (3) is particularly likely to be a dimer fatty acid. Experts know that a dimer fatty acid is a mixture of different acids. The predominant structures are as follows (especially after hydrogenation of the double bonds).

[0077] ^OÖC ' ■

[0078]

[0079] 2025PF30027- Abroad

[0080]

[0081] Fully hydrogenated compounds are preferably used in this process. Dimer fatty acids are generally mixtures. A fatty acid with conjugated double bonds (conjugated acid) is reacted with other unsaturated fatty acids. Conjugated linoleic acids are particularly preferred for this purpose. The reaction typically proceeds via Diels-Alder addition, forming a partially unsaturated C6 ring. Thus, dimer fatty acids initially contain at least one or more double bonds. The mixture of dimer fatty acids can include trimers and monomers of the fatty acids in addition to the dimer. Oleic acid and linoleic acid are particularly preferred for the reaction. The double bonds contained in the dimer fatty acid are generally hydrogenated.

[0082] Formula (3) is particularly preferred as a dimer fatty acid with 36 carbon atoms.

[0083] Dimer fatty acids are commercially available and known, for example, under the trade names Pripol 1009, Pripol 1006, Pripol 1025, Radiacid 0960, Radiacid 0975, Radiacid 0976, Radiacid 0977, Radiacid 0978, and Unidyme 18. Pripol and Pripol derivatives are produced, as described above, by the oligomerization of unsaturated fatty acids—preferably C18 acids. Dimerization yields a mixture of mono-, di-, and tricarboxylic acids. The monofunctional compounds are usually separated by distillation. Typically, a mixture of 80% difunctional and 20% trifunctional compounds is obtained, which is further purified by distillation to enrich the difunctional compounds. Hydrogenation then yields the saturated compounds. Pripol as a dimer fatty acid is a purified mixture comprising predominantly C36 diacid.

[0084] The esterification in process step (i) yields a compound (A) that has at least two ester groups. This means that the dicarboxylic acid reacts essentially with both acid groups. As a result, an acid number of less than 10 mg KOH / g can be achieved according to the invention. The compound (A), which has at least two ester groups, preferably has an acid number of less than 9 mg KOH / g, and particularly preferably less than 5 mg KOH / g. In this context 2025PF30027- Abroad

[0085] - 16 - It is evident that the term "less than" generally means a range from 0 mg KOH / g up to the specified number. A range greater than 0 mg KOH / g up to the specified number is particularly preferred. Preferably, the acid number of compound (A) is determined according to ISO 2114:2000. It has been found that when the acid number is within the range according to the invention, the process is particularly environmentally advantageous. In particular, the process has a good carbon balance. In process step (i), the esterification essentially produces water, and in process step (ii), only a few acid groups remain, which can then react, if necessary, with the diaryl carbonate and / or dialkyl carbonate, releasing carbon dioxide. Thus, with the acid number according to the invention, only a very small proportion of carbon is lost as carbon dioxide.

[0086] Process step (i) is preferably carried out in the presence of at least one catalyst. Equally preferred is the at least one catalyst being selected from the group consisting of organo-zinc or tin compounds. The use of this type of catalyst is known in the prior art. Among the catalysts preferred in the present invention are zinc acetate, butyltin tris-2-ethylhexanoate, dibutyltin diacetate, and / or dibutyltin oxide. Other catalysts may include those based on titanium, zinc, manganese, lithium, germanium, and cobalt. Titanium tetraisopropoxide, titanium butoxide, magnesium acetate, antimony oxide, antimony triacetate, or any mixtures thereof are particularly preferred. The catalyst amounts can range from 10 ppm to 20,000 ppm or from 10 to 10.000 ppm, or 10 to 5000 ppm, or 10 to 1000 ppm, or 10 to 500 ppm, or 10 to 300 ppm, or 10 to 250 ppm are sufficient, based on the catalyst and based on the weight of the product of process step (i). It is important to ensure that the catalyst used in process step (i) does not have an adverse effect on the reaction or on the resulting polyester carbonate in process step (ii). As the examples according to the invention show, the catalyst from process step (i) can also be used in process step (ii) to build up molecular weight.

[0087] Process step (i) can be carried out in solution or in the substance. It can, for example, also be carried out azeotropically. Preferably, process step (i) is carried out in the melt. It is particularly preferred that the water formed is removed. The removal of the water can preferably be carried out by distillation or vacuum. Particularly preferably, the removal of the water formed is first carried out by distillation followed by the application of a vacuum. It is important to ensure that the vacuum is not too low so that no 1,4:3,6-dianhydrohexitol and / or tricyclodecanedimethanol is removed from process step (i). In this case, however, the lost 2025PF30027- Abroad can also be determined by measuring the OH number and the acid number.

[0088] - 17 - Quantity calculated and balanced. The process according to the invention has the particular advantage that it is a well-controlled reaction. This means, in particular, that the stoichiometry for process step (ii) can continue to be precisely adjusted by tracing the acid number and, if applicable, the OH number. This can be achieved, for example, by adding further components in process step (i) and / or (ii). Overall, polyester carbonates can thus be produced in a very targeted manner.

[0089] Furthermore, the inventive process step (i) preferably comprises at least one, and particularly preferably all, of the following steps (ia) to (ic):

[0090] (ia) Melting all components present in process step (i), i.e., at least the dicarboxylic acid and the 1,4:3,6-dianhydrohexitol and / or the tricyclodecanedimethanol, optionally in the presence of at least one catalyst. This is preferably carried out under a protective gas atmosphere, preferably under nitrogen and / or argon. Preferably, step (ia) is carried out in the absence of a solvent. The term "solvent" is known to those skilled in the art in this context. According to the invention, the term "solvent" is preferably understood to mean a compound that does not undergo any chemical reaction in process steps (i) and / or (ii). Excluded are those compounds that are formed by the reaction (for example, water from the esterification reaction of process step (i)). The solvent can also act as an entrainer to remove the water formed azeotropically.Of course, it cannot be ruled out that the starting compounds contain traces of solvents. According to the invention, this case is preferably included. However, according to the invention, an active step of adding such a solvent is preferably avoided, since this must be removed before process step (ii). Furthermore, the solvent can also complicate the determination of the OH and / or acid number.

[0091] (ib) Heating the mixture, preferably the melt obtained from step (ia). Step (ia) and step (ib) may overlap, since heating may also be necessary to produce a melt in step (ia). The heating is preferably carried out first to 100 °C to 250 °C.

[0092] (ic) Reaction of the mixture, preferably the mixture obtained from step (ib) by introducing mixing energy, preferably by stirring. Here too, step (ic) can overlap with step (ib), since the reaction of the mixture can already be initiated by heating. Preferably, the melt is already heated to temperatures between 100 and 250 °C under normal pressure by step (ib). Depending on the catalyst chosen, the temperature can be kept in the range of 160–200 °C. Alternatively, the temperature is gradually increased in step (ic) – depending on the observed reactivity – to 200–300 °C, preferably 210–260 °C, and particularly preferably 215–255 °C.

[0093] - 18 -increased. It is preferred that the temperature is only high enough to allow the water produced to be removed from the mixture at temperatures below 100 °C (at atmospheric pressure). In principle, higher temperatures are also possible in this step; however, side reactions (e.g., discoloration) can occur at higher temperatures. Therefore, higher temperatures are less preferred. Preferably, process step (ic) is carried out at atmospheric pressure, during which the water produced is distilled off. The reaction time of this process step can be controlled by adjusting the temperature. Preferably, a vacuum is then applied to remove any remaining water from the process step and, if necessary, to shift the equilibrium of the esterification reaction until the desired acid number, as defined according to the requirements, is reached.

[0094] The reaction time in step (ic) depends on the amount of reactants, in particular the catalyst, the temperature profile used and possibly also the stirring conditions.

[0095] Process step (i) can be carried out either batchwise or continuously. Due to the reaction time, it can be advantageous to carry out process step (i) batchwise. Therefore, it is preferred that process step (i) be carried out batchwise. All reactors familiar to those skilled in the art are suitable for this purpose. If the process is carried out continuously, process step (i) could, for example, be carried out in a tubular reactor. If the process is carried out batchwise, the use of a stirred tank reactor is particularly suitable. It is possible that after process step (i), the compound (A) is first isolated and optionally purified. It is also possible that the mixture, as obtained after process step (i), is used directly in process step (ii). This is preferred because it is less complex and therefore economically and ecologically advantageous.In particular, if the mixture obtained after process step (i) is directly used in process step (ii), it is also possible to adjust the stoichiometry for process step (ii). Diols can be removed in process step (i) by vacuum. The amount lost can be determined via the OH number. It can be compensated for by adding components in process step (i) or (ii). Either a dicarboxylic acid can be added if little diol was removed, or diol can be added if a large amount of diol was removed. It can also be advantageous to start with an excess of diol in process step (i) to avoid active compensation. Compound (A) has at least two ester groups. However, it is also possible that compound (A) is a mixture of different compounds, all of which have at least two ester groups.It is evident to the expert that if the acid number is greater than 0 mg KOH / g, compounds must also be present which have only one or no ester groups at all. These are considered impurities in this context. If compound (A) has more than two 2025PF30027- foreign.

[0096] - 19 - If the compound has ester groups, an oligoester (i.e., a trimer, tetramer, or larger) is generally formed. Thus, compound (A) can also be a mixture of different oligoesters. Preferably, this oligoester has a number of repetitions of 1 to 10, more preferably 1 to 7, and most preferably 1 to 5. A person skilled in the art can determine the corresponding molecular weight. To obtain an acid number in the range defined according to the invention, the initial acid number of the dicarboxylic acid must be known. A person skilled in the art can calculate the acid number of compound (A) using the initial acid number. For this purpose, the required amounts of the dicarboxylic acid and the 1,4:3,6-dianhydrohexitol and / or tricyclodecanedimethanol must be known. The actual acid number of compound (A) can be determined at the end of the reaction.

[0097] If purification and / or isolation of compound (A) takes place after process step (i) and before process step (ii), the composition of the mixture of compound (A) may change in a manner apparent to a person skilled in the art. It is particularly preferred that compound (A) in process step (ii) has an acid number of less than 10 mg KOH / g, preferably less than 9 mg KOH / g, and most preferably less than 5 mg KOH / g. Alternatively, a person skilled in the art can calculate the desired OH number of the mixture based on the composition of diols and dicarboxylic acids in order to make any necessary corrections and determine the required amount of reagents for process step (ii).

[0098] Procedure step (ii)

[0099] In process step (ii) according to the invention, compound (A) reacts with at least one diaryl carbonate and / or dialkyl carbonate to form a polyester carbonate. Preferably, compound (A) is used immediately after process step (i). This means that compound (A) is not subjected to isolation from the reaction mixture of process step (i). It is also possible for compound (A) to be isolated from the reaction mixture of process step (i) in process step (ii). In this case, it is additionally preferred that compound (A) be purified.

[0100] In process step (ii), at least one reaction of the OH groups of compound (A) with the diaryl carbonate and / or dialkyl carbonate takes place. This reaction is generally also referred to as condensation or upcondensation. The term "condensation" or "upcondensation" is familiar to those skilled in the art. Preferably, "condensation" is understood to mean a reaction in which two molecules (of the same substance or different substances) combine to form a larger molecule, with one molecule of a chemically simple substance being eliminated. This compound eliminated during condensation is preferably removed in process step (ii). 2025PF30027- Abroad

[0101] - 20 - Preferably, in process step (ii) a reaction of compound (A) with at least one diaryl carbonate takes place.

[0102] Furthermore, it is preferred that the diaryl carbonate of process step (ii) is selected from the group consisting of a compound of formula (7)

[0103] RR

[0104]

[0105] wherein R, R' and R'' can each be the same or different independently of one another and represent hydrogen, optionally branched Ci-C34-alkyl, Cy-C alkylaryl, Ce-C34-aryl, a nitro group, a carbonyl-containing group, a carboxyl-containing group or a halogen group.

[0106] Particularly preferred is the at least one diaryl carbonate diphenyl carbonate, 4-tert-butylphenyl phenyl carbonate, di-(4-tert-butylphenyl) carbonate, biphenyl-4-yl phenyl carbonate, di-(biphenyl-4-yl) carbonate, 4-(1-methyl-1-phenylethyl)phenyl phenyl carbonate, di-[4-(1-methyl-1-phenylethyl)phenyl] carbonate, bis(methyl salicyl) carbonate, bis(ethyl salicyl) carbonate, bis(propyl salicyl) carbonate, bis(2-benzoyl phenyl carbonate), bis(phenyl salicyl) carbonate and / or bis(benzyl salicyl) carbonate. The at least one diaryl carbonate is particularly preferably diphenyl carbonate, 4-tert-butylphenyl phenyl carbonate, di-(4-tert-butylphenyl) carbonate, biphenyl-4-yl phenyl carbonate, di-(biphenyl-4-yl) carbonate, 4-(l-methyl-1-phenylethyl) phenyl phenyl carbonate, and / or di-[4-(l-methyl-l-phenylethyl) phenyl] carbonate. The at least one diaryl carbonate is particularly preferably diphenyl carbonate.

[0107] Furthermore, it is preferred that at least one catalyst is present in process step (ii). This is preferably one of the catalysts mentioned in process step (i) or a basic catalyst. Any inorganic or organic basic compounds are suitable as a basic catalyst.

[0108] Examples of basic catalysts include lithium, sodium, potassium, cesium, calcium, barium, magnesium, hydroxides, carbonates, halides, phenolates, diphenolates, fluorides, acetates, phosphates, hydrogen phosphates, boranates, nitrogen and phosphorus bases such as tetramethylammonium hydroxide, tetramethylammonium acetate, tetramethylammonium fluoride, tetramethylammonium tetraphenylboranate, tetraphenylphosphonium fluoride, tetraphenylphosphonium tetraphenylboranate, dimethyl diphenylammonium hydroxide, and tetraethyl 2025PF30027- Abroad

[0109] ammonium hydroxide, cethyltrimethylammonium tetraphenylboranate, cethyltrimethylammonium phenolate, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) or guanidine systems such as 1,5,7-triazabicyclo[4,4,0]-dec-5-ene, 7-phenyl-1,5,7-triazabicyclo[4,4,0]-dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4,4,0]-dec-5-ene, 7,7'-hexylidenedi-1,5,7-triazabicyclo[4,4,0]-dec-5-ene, 7,7'-Decylidene di-1,5,7-triazabicyclo-[4,4,0]-dec-5-ene, 7,7'-Dodecylidene di-1,5,7-triazabicyclo-[4,4,0]-dec-5-ene, or phosphazenes such as the phosphazene base Pl-t-Oct = tert-octyl-imino-tris-(dimethylamino)-phosphorane, phosphazene base Pl-t-Butyl = tert-butyl-imino-tris-(dimethylamino)-phosphorane, BEMP = 2-tert-butylimino-2-diethylamino-1,3-dimethyl-perhydro-1,3,2-diaza-2-phosphorane. Phosphonium catalysts of formula (K) are also particularly suitable.

[0110] R d

[0111] PR a

[0112]

[0113] (K)

[0114] where R a , R b , R c and R d The same or different Cl-C10 alkyls, C6-C14 aryls, C7-C15 arylalkyls or C5-C6 cycloalkyls, preferably methyl or C6-C14 aryls, particularly preferably methyl or phenyl, and A" can be an anion such as hydroxide, sulfate, hydrogen sulfate, hydrogen carbonate, carbonate or a halide, preferably chloride or an alkylate or arylate of the formula -OR, wherein R can be a C6-C14 aryl, C7-C15 arylalkyl or C5-C6 cycloalkyl, preferably phenyl.

[0115] Particularly preferred catalysts are tetraphenylphosphonium chloride, tetraphenylphosphonium hydroxide and tetraphenylphosphonium phenolate; tetraphenylphosphonium phenolate is especially preferred.

[0116] These catalysts are preferably used in quantities of 10' 2 up to 10' 8Mole, based on 1 mol of all compounds containing OH groups, is used. It is additionally preferred that an alkaline salt is also present as a cocatalyst. The amounts of the alkaline salts used as cocatalysts can be in the range of 1 to 500 ppb, preferably 5 to 300 ppb, and particularly preferably 5 to 200 ppb.

[0117] The catalyst can be used alone or as a catalyst mixture and can be added in substance or as a solution, for example in water or in phenol, e.g. as a mixed crystal with phenol. 2025PF30027- Abroad

[0118] - 22 - Catalysts already described in process step (i) can also be used. Organo-zinc or tin compounds are particularly preferred. Dibutyltin dilaurate, dibutyltin oxide, di-n-octyltin oxide, monobutyltin oxide, tin(II) ethylhexanoate, and / or titanium(IV) butoxide are particularly preferred. The catalyst amounts can range from 10 ppm to 20,000 ppm, or 10 to 10,000 ppm, or 10 to 5,000 ppm, or 10 to 1,000 ppm, or 10 to 500 ppm, or 10 to 300 ppm, or 10 to 250 ppm, based on the catalyst metal and based on the weight of the product of process step (i) used in process step (ii). It is particularly preferred that in the inventive process step (ii) 0.9 to 1.1, particularly preferably 0.95 to 1.05 moles of diaryl carbonate are used for 1 mol of compound (A) and optionally for all other diols.

[0119] According to the invention, it is particularly preferred that at least one additional diol is present in process step (ii). This diol can be either 1,4:3,6-dianhydrohexitol and / or tricyclodecanedimethanol or another diol. If this diol is 1,4:3,6-dianhydrohexitol and / or tricyclodecanedimethanol, it can also be added to process step (ii) along with compound (A). In particular, it can also be 1,4:3,6-dianhydrohexitol and / or tricyclodecanedimethanol that did not react in process step (i).

[0120] The method according to the invention is preferably characterized in that the at least one additional diol is aliphatic or cycloaliphatic. The process according to the invention is particularly preferably characterized in that the at least one additional diol is selected from the group consisting of 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2-bis(4-hydroxycyclohexyl)propane, tetrahydro-2,5-furandimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, cyclobutane-1,1-diyldimethanol, and 8-(hydroxymethyl)-3-tricyclo[5.2.1.02,6]decanyl]methanol, 2-butyl-2-ethyl-1,3-propanediol, 2-(2-hydroxyethoxy)ethanol, 2,2,4-Trimethyl-1,3-pentanediol, 2,2-Dimethylpropane-1,3-diol, 1,2-Propanediol, 1,3-Propanediol, 1,4-Butanediol, 1,5-Pentanediol, 1,6-Hexanediol, 1,8-Octanediol, 1,4:3,6-Dianhydrohexitol and a compound of formula (4),

[0121] HO— (C H2) r — R 3- (C H2) s - OH

[0122] (4)

[0123] where each r and each s independently represents a number between 0 and 4, and each R 3 independently of each other stands for a structure of the formulas (R3A), (R3B), (R3C) and (R3D) 2025PF30027- Abroad

[0124] - 23 -

[0125] (R3C),

[0126]

[0127] (R3D),

[0128] where the positions marked with , in formulas (R3A) to (R3D) are the positions where the (CfFf group shown in formula (4) is located.

[0129] Particularly preferred is the at least one additional diol selected from the group consisting of 1,4:3,6-dianhydrohexitol and a compound of formula (4), wherein in formula (4) each r and each s are independently selected for a number between 0 and 2, most preferably for 0 or 1, each R 3independently of each other stands for a structure of the formulas (R3A) and a is 0 or 1.

[0130] Furthermore, according to the invention, it is not excluded that aromatic diols are present in process step (ii). Preferably, however, these are present only in small proportions. Particularly preferably, up to 20 mol%, more preferably up to 10 mol%, and most preferably up to 5 mol% of an aromatic diol compound are present in process step (ii) with respect to the total amount of substance of the diol compound used (which also includes the diols present in process step (i)). In these cases, according to the invention, it is still preferably referred to as an aliphatic polyester carbonate. However, it is particularly preferred that no aromatic diol compound is used in process step (ii). As a rule, aromatic compounds in polyester carbonates reduce their UV stability and weather resistance. This is particularly disadvantageous for outdoor applications. Moreover, aromatic components reduce the UV stability and weather resistance of polyester carbonates.

[0131] - 24 - Polyester carbonate affects the surface hardness of molded bodies produced from it, which may necessitate painting.

[0132] These additional aromatic diol compounds are preferably selected from the group consisting of bisphenol A, 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-dihydroxybiphenyl (DOD), 4,4'-dihydroxybiphenyl ether (DOD ether), bisphenol B, bisphenol M, and bisphenols (I) to (III).

[0133]

[0134] In these formulas (I) to (III) R' stands for Cl-C4-alkyl, aralkyl or aryl, preferably for methyl or phenyl, most preferably for methyl.

[0135] By using an additional diol in process step (ii), it is possible to control whether the resulting polyester carbonate is amorphous and / or remains so. Furthermore, the glass transition temperature can be influenced by this additional diol. The polyester carbonate according to the invention, or that obtained by the process according to the invention, has a glass transition temperature of at least 90 °C. Particularly preferably, the polyester carbonate has a glass transition temperature of at least 95 °C, more preferably at least 100 °C, and most preferably at least 110 °C. The glass transition temperature (Tg) can preferably be determined by differential scanning calorimetry (DSC) in accordance with DIN EN ISO 11357-1:2009-10 and ISO 11357-2:2013-05. In particular, a heating rate of 20 K / min under nitrogen is used, and the Tg is determined as the inflection point in the second heating process.A glass transition temperature within the defined range enables the polyester carbonate according to the invention to be used in common plasticizing processes (e.g. injection molding, (co)extrusion, blow molding, thermoforming).

[0136] It is evident to a person skilled in the art how the starting materials, in particular the dicarboxylic acid, the diaryl carbonate, the 1,4:3,6-dianhydrohexitol and / or the tricyclodecanedimethanol (and optionally further diols) are used in process steps (i) and (ii) to obtain a polyester carbonate of the desired composition. It is particularly preferred that, in the process according to the invention, 8 mol% to 40 mol% of at least one dicarboxylic acid, in particular 2025PF30027- Abroad

[0137] - 25 - preferably 15 to 35 mol-% of at least one dicarboxylic acid based on the total amount of dicarboxylic acid, optionally with additional diols and the 1,4:3,6-dianhydrohexitol and / or tricyclodecanedimethanol.

[0138] It is also preferred that in the process according to the invention, 2 to 14 mol%, particularly preferably 3 to 12 mol%, and most preferably 3.5 to 7.5 mol% of at least one dicarboxylic acid, particularly preferably a dimer fatty acid, are used, based on the total amount of dicarboxylic acids used, optionally with additional diols and 1,4:3,6-dianhydrohexitol and / or tricyclodecanadimethanol. It is particularly preferred that 1,4:3,6-dianhydrohexitol is used in process step (i) (and not tricyclodecanadimethanol).Furthermore, it is then preferred that in process step (ii) 4 to 25 mol%, particularly preferably 5 to 20 mol%, equally preferably 7 to 18 mol% and most preferably 10 to 15 mol%, most preferably 5 to 10 mol% or equally preferably 8 to 12 mol% of at least one further diol, particularly preferably tricyclodecanedimethanol, be used, based on the total amount of dicarboxylic acids used, optionally further diols and 1,4:3,6-dianhydrohexitol and tricyclodecanedimethanol. Furthermore, it is preferred that at least 55 mol%, particularly preferably at least 65 mol%, equally preferably at least 75 mol% and most preferably at least 80 mol% of the 1,4:3,6-dianhydrohexitol, particularly preferably isosorbide, be used, based on the total amount of dicarboxylic acids used, optionally further diols and 1,4:3,6-dianhydrohexitol and / or tricyclodecanadimethanol.The use of dimer fatty acid, 1,4:3,6-dianhydrohexitol and tricyclodecanedimethanol, especially in the specified quantities, has the advantage of producing a polyester carbonate which exhibits good stability against water, preferably hot water stability, as well as good grease resistance, and good resistance to lipid solutions and organic solvents, along with good processability and good UV and weather stability.

[0139] Preferably, the polyester carbonate obtained according to the inventive method has a relative solution viscosity above 1.20, particularly preferably from 1.21 to 1.65, further preferably from 1.22 to 1.63, particularly preferably from 1.23 to 1.62, and most preferably from 1.26 to 1.55. 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 in accordance with DIN 51562-3; 1985-05. The flow times of the polyester 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, a calibration of the 2025PF30027- Abroad is first performed.

[0140] - 26 - Ubbelohde viscometers are calibrated using measurements of the pure solvents dichloromethane, trichloroethylene, and tetrachloroethylene (always at least 3 measurements, at most 9 measurements). The actual calibration is then performed using dichloromethane. Subsequently, the polymer sample is 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.

[0141] It is preferred that the chemical compound(s) released during condensation be removed in process step (ii) by means of a vacuum. Accordingly, it is preferred that the process according to the invention is characterized in that the chemical compound(s) released during condensation are separated in process step (ii) by a stepwise reduction of the pressure. A stepwise separation is preferably chosen when different volatile components are to be separated. A stepwise separation is also preferably chosen to ensure the most complete possible separation of the volatile component(s). The volatile components are the chemical compound(s) released during condensation. This is in particular the aryl alcohol formed, especially phenol.

[0142] A gradual reduction of the pressure can be achieved, for example, by lowering the pressure as soon as the head temperature drops, in order to ensure the continuous removal of the chemical compound released during condensation. When a pressure of 1 mbar, preferably < imbar, is reached, condensation continues until the desired viscosity is achieved. This can be accomplished, for example, by torque control; that is, the polycondensation is stopped when the desired stirrer torque is reached.

[0143] The separation of the condensation product in process step (ii) preferably takes place at temperatures of 180 °C to 320 °C, more preferably 190 °C to 280 °C, more preferably 195 °C to 260 °C, and more preferably 200 °C to 250 °C. Furthermore, the vacuum during separation is preferably 500 mbar to 0.01 mbar. It is particularly preferred that the separation is carried out stepwise by reducing the vacuum. Most preferably, the vacuum in the last stage is 10 mbar to 0.01 mbar.

[0144] Process step (ii) can be carried out batchwise or continuously. Preferably, process step (ii) is carried out continuously. During process step (ii), a viscosity increase occurs. Above a certain viscosity / molecular weight, condensation in a stirred tank may no longer be efficient, as the surface renewal decreases and the removal of the low-molecular-weight condensation products (especially phenol) becomes more difficult. 2025PF30027- Abroad

[0145] - 27 - Therefore, it is particularly useful to carry out process step (ii) in a process unit such as a high-viscosity reactor, disk or grid reactor, extruder, or thin-film evaporator. However, it is also possible to carry out process step (ii) in a stirred tank, possibly even the same stirred tank as in process step (i), provided it has appropriately suitable stirring tools.

[0146] In another aspect of the present invention, a compound of formula (5) is provided,

[0147]

[0148] (5)

[0149] where in formula (5) each A independently represents formula (5a) or (5b),

[0150]

[0151] (5a), (5b),

[0152] where the where the with

[0153]

[0154] The marked positions in formulas (5a) and (5b) are the positions where the oxygen atoms shown in formula (5) are located, adjacent to A.

[0155] each R 2 independently of each other stands for an aliphatic group with 16 to 44 carbon atoms, which may contain one or more double bonds and

[0156] n represents a number from 1 to 10, preferably 1 to 7, particularly preferably 1 to 5.

[0157] The compound of formula (5) is one of the possible compounds (A) that can be formed by the inventive process step (i). Preferably, the compound of formula (5) is obtained by the inventive process, particularly preferably by the preferred embodiments of the inventive process, possibly also in all combinations of the preferred embodiments.

[0158] The compound of formula (5) according to the invention has the particular advantage of being OH-terminated. This means that it can be used in a process for the production of a polyester carbonate like a classic diol. The reactivity of the compound of formula (5) in a polycondensation with a diaryl carbonate and / or dialkyl carbonate is comparable to other diols. This facilitates the incorporation of the compound of formula (5) into a polyester carbonate.

[0159] - 28 -control. At the same time, ester groups are also incorporated into the polyester carbonate by the compound of formula (5). Here, the potentially different reactivity of components that are to be incorporated into the polyester carbonate can be compensated for by using the compound of formula (5).

[0160] R is particularly preferred 2 represented in formula (5) by the following formula (R2A)

[0161] CH3

[0162] R 11

[0163] - RU—Y—RU - I

[0164] R 11

[0165] I

[0166]

[0167] CH3 (R2A),

[0168] where Y represents a bridging structure selected from the group consisting of an alkylene group with 1 to 4 carbon atoms, an alkylidene group with 1 to 4 carbon atoms, and a cycloalkylene group with 4 to 12 carbon atoms, wherein the cycloalkylene group optionally contains one or more double bonds and / or is optionally fused to one or more further cycloalkylene groups, wherein the one or more further cycloalkylene groups optionally each have one or more double bonds.

[0169] where the R adjacent to the bridging structure 11 -groups are bound to any position of the bridging structure and

[0170] where each R 11independently of each other stands for an alkylene group with 1 to 12 carbon atoms or an alkylidene group with 1 to 12 carbon atoms, with the proviso that the structure of formula (R2A) comprises 16 to 44 carbon atoms and wherein the with ,

[0171]

[0172] The marked positions in formula (R2A) are the positions where the (C=O) groups shown in formula (5) are located, which are attached to R 2 adjacent.

[0173] Formula (R2A) is particularly preferred, represented by one of the formulas shown above (R2Aa), (R2Ab), (R2Ac) or (R2Ad). Any R is particularly preferred. 11in formula (R2A) and / or in formulas (R2Aa), (R2Ab), (R2Ac) or (R2Ad) independently for an alkylene group with 1 to 10 carbon atoms, provided that the structure of formula (R2A) and / or in formulas (R2Aa), (R2Ab), (R2Ac) or (R2Ad) comprises 16 to 44 carbon atoms. The preferences described above for formula (3) in group R are particularly preferred. 2 or R 11 and / or Y.2025PF30027- Abroad

[0174] - 29 - The person skilled in the art can determine the arithmetic mean of repeat units n by known methods. In particular, n can be determined by gel permeation chromatography. Particularly preferably, n is determined by gel permeation chromatography in tetrahydrofuran with a polystyrene as a standard. This yields different peaks, which can be assigned to corresponding oligomers based on their molecular weight. If the peaks are not clearly separated (especially in the case of longer-chain oligomers), the division of the peaks can preferably be set at the nadir between two peaks. If no nadir is measured, the tailing of the peak is preferably still counted as the corresponding repeat unit of the maximum. Figure 1 shows an example chromatogram of a compound of formula (5), where A represents formula (5a) and R 2is derived from dimer fatty acids. As this chromatogram shows, compounds can be distinguished where n = 1, n = 2 and n = 3.

[0175] In another aspect of the present invention, a polyester carbonate is provided comprising the structural unit of formula (6)

[0176]

[0177] (6)

[0178] where in formula (6)

[0179] Z always stands for either formula (5a) or formula (5b),

[0180] Each A independently represents formula (5a) or (5b),

[0181]

[0182] (5a), (5b),

[0183] where the where the with

[0184]

[0185] The marked positions in formulas (5a) and (5b) are the positions where the oxygen atoms shown in formula (6) are located, which are adjacent to A or Z,

[0186] the positions marked with in formula (6) are the positions at which formula (6) is incorporated into the polyester carbonate,

[0187] each R 2 independently of each other stands for an aliphatic group with 16 to 44 carbon atoms, which may contain one or more double bonds and

[0188] n represents a number from 2 to 10, preferably 2 to 7, particularly preferably 2 to 5. 2025PF30027- Abroad

[0189] - 30 - The person skilled in the art understands the connection between the polyester carbonate according to the invention and the process according to the invention. Preferably, the polyester carbonate of formula (6) is obtained by the process according to the invention, particularly preferably by the preferred embodiments of the process according to the invention, possibly also in all combinations of the preferred embodiments.

[0190] The preferences described above, or combinations thereof, are preferred for R. 2 .

[0191] The polyester 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, particularly preferably from 1.23 to 1.62, and most preferably from 1.26 to 1.55. The relative solution viscosity is preferably determined as described above.

[0192] The number of repeat units n can be determined by the expert. For this purpose, n is first determined by the synthesis of compound (A). For example, n can be determined for compound (A) using GPC. Also in the 13 The peaks in the 1C and / or 1H NMR spectra can be assigned to the different bonds. A polyester carbonate comprising formula (6) always exhibits, due to n = at least 2, either formula (5a) or formula (5b), which is surrounded by two carbon atoms of an ester bond. It also exhibits two characteristic CH or CH2 groups next to the ester groups, which are visible in 1H NMR. These exhibit a different chemical shift than a compound of formula (5a) or formula (5b) bonded to a carbonate group. By comparing the spectra of compound (A) and the polyester carbonate, at least these groups can be detected. The determination of n can be supported, for example, by MALDI-TOF mass spectrometry.

[0193] The polyester carbonate according to the invention particularly preferably has structures of formula (8), wherein

[0194]

[0195] where A has the meanings given for formula (6), the positions marked with the positions in formula (6) are the positions at which formula (6) is incorporated into the polyester carbonate, and m represents the average number of repeating units. 2025PF30027- Abroad

[0196] - 31 - Preferably m is 2 to 500, particularly preferably 3 to 300, most particularly preferably 3 to 200. The person skilled in the art can determine this m in a manner known to them, for example by NMR and / or GPC.

[0197] The polyester carbonate according to the invention is particularly preferably characterized in that it consists of at least 80 wt.%, particularly preferably at least 85 wt.%, and more preferably at least 90 wt.% of structures of formula (6) and / or (8).

[0198] In particular, when the polyester carbonate according to the invention is obtained by the process according to the invention, it has a specific structure because it was produced sequentially. Thus, the polyester carbonate comprises specific, targeted, and controlled linkages of the monomers via ester groups and similarly targeted linkages via carbonate groups. This allows the property profile of the polyester carbonates according to the invention to be specifically influenced. It is particularly preferred that the polyester carbonate according to the invention and / or the polyester carbonate obtained by the process 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" means that the chemical compound in question is accessible, obtainable, and / or preferably such a renewable and / or regenerative raw material at the filing date. A renewable and / or regenerative raw material is preferably understood to be a raw material that is regenerated by natural processes at a rate comparable to its degradation rate (see CEN / TS 16295:2012). The term serves in particular to distinguish it from raw materials derived from fossil resources, also referred to as petro-based. Whether a raw material is bio-based or petro-based can be determined by measuring carbon isotopes in the raw material, since the relative amounts of the carbon isotope C... 14lower in fossil raw materials. This can be done, for example, according to ASTM D6866-18 (2018), ISO 16620-1 to -5 (2015), or DIN SPEC 91236 2011-07. According to the invention, the term "bio-based" is preferably used for compounds which have a C 14 Isotopic content of over 0.1 x 10⁻¹⁰ 12 , especially preferred from over 0.2 x 10' 12 , and especially preferred by those over 0.3 x 10 12 exhibit these characteristics. In particular, isosorbide and dimer fatty acids are bio-based.

[0199] Furthermore, the polyester carbonate according to the invention exhibits good water resistance, preferably hot water resistance, as well as good grease resistance, and good resistance to lipid solutions and organic solvents, combined with good processability and good UV and weather resistance. 2025PF30027- Abroad

[0200] - 32 - Furthermore, it is advantageous to produce the polyester carbonate according to the invention using the process according to the invention, since the carbon balance is particularly favorable.

[0201] The carbon balance of a prior art polyester carbonate is compared below with that of the polyester carbonate of the present invention (or obtained according to the inventive process). It is assumed that the polyester carbonate is produced from 85.5 mol% isosorbide, 4.5 mol% dimer fatty acid, and 10 mol% tricyclodecanedimethanol. It is irrelevant whether the dimer fatty acid is first esterified with isosorbide and / or tricyclodecanedimethanol and then the other diol is added, or whether a mixture of isosorbide and tricyclodecanedimethanol is added in process step (ii). For better comparability, it is first reacted with isosorbide in the following.

[0202] First, a dimer fatty acid diphenyl ester (DFA-DP) is produced by reacting dimer fatty acid (DFA) with diphenyl carbonate (DPC) according to the following reaction:

[0203]

[0204] DFA + 2 DPC DFA-DP + 2 phenol + 2 CO2

[0205] This process produces 0.02 kg of CO2 per kg of polyester carbonate. The DFA-DP is then reacted with DPC and other diols to form a polyester carbonate. Phenol is released during this reaction.

[0206] In the process according to the invention, a dimer fatty acid oligoester (DFA oligoester) would first be formed from the reaction of isosorbide (ISB) and DFA according to the following reaction:

[0207] DFA +2 ISB DFA oligoester + 2 H2O

[0208] In a further process step according to the invention, the DFA oligoester is reacted with, for example, DPC to form a polyester carbonate (in this example in the presence of TCD). Phenol is released in this process.

[0209] Thus, in the specific example mentioned above, the process according to the invention can save 0.02 kg CO2 per 1 kg polyester carbonate in the case of complete esterification of the DFA with ISB. Depending on the starting materials and the acid number achieved in process step (i), more than 90-95% of this 0.02 kg CO2 per 1 kg polyester carbonate can be saved, in addition to the phenol.

[0210] In another aspect of the present invention, a molding compound is provided, containing the polyester carbonate according to the invention. Likewise, a molded body containing the polyester carbonate according to the invention is provided. The molded bodies according to the invention can be produced, for example, by injection molding, extrusion, and blow molding processes. [Further details omitted]

[0211] - 33 - The processing method is the production of shaped bodies by deep drawing from previously manufactured sheets or films.

[0212] Brief description of the characters:

[0213] Figure 1: GPC spectrum of a compound (5) with A = formula (5a) and R 2 is derived from dimer fatty acid (darker line) and GPC spectrum of dimer fatty acid (unreacted) (lighter line). The peak at approximately 2.45 kDa is ISB. The GPC was recorded using GPC method I. Figure 2: 'H-NMR spectrum of compound (A) of example 22025PF30027- Ausland'

[0214] - 34 - Examples

[0215] Acid number (AN):

[0216] The acid number was measured titrimetrically according to ISO 2114:2000 and is expressed as the mass of potassium hydroxide (KOH) in milligrams required to neutralize one gram of the test substance. It thus indicates the concentration of the carboxyl groups present.

[0217] Hydroxyl number (OHZ):

[0218] The hydroxyl concentration (OHC) was measured titrimetrically in tetrahydrofuran as solvent according to ISO 4629-2:2016 [catalyzed version with tetrahydrofuran instead of N-methyl2-pyrrolidone (NMP)]. The OHC is expressed as the mass of potassium hydroxide (KOH) in milligrams required to neutralize one gram of the test substance. It indicates the concentration of hydroxyl groups present.

[0219] Gel permeation chromatography I:

[0220] The number-mean molecular weight (Mn) and weight-mean molecular weight (Mw) of compound (A) were measured by size exclusion chromatography (SEC), calibrated with a series of polystyrene standards with a molecular weight range of 500 to 7 x 10 6g / mol. Stabilized tetrahydrofuran [THF with 0.007-0.015% w / w butylhydroxytoluene (BHT)], modified with 0.8% acetic acid, was used as the eluent at a flow rate of 1 mL / min at 40°C. Specifically, 50 mg of a solid sample was dissolved in 5 mL of eluent for 16 hours at room temperature without shaking.

[0221] The solution thus prepared was then filtered through a VWR spray filter [European article number 514-0071; PTFE (polytetrafluoroethylene) spray filter, 25 mm diameter, 0.45 pm pore size] from VWR International, LLC. 10 pL of the solution thus prepared after filtration was injected into the system for measurement. The GPC measurements were performed on a Waters Acquity APC system consisting of the following components:

[0222] 1. a Waters Acquity UPLC RI refractive index detector at 40°C

[0223] 2. a Waters Acquity APC Column Manager - S with three different Acquity APC columns (450µm, 125µm and 45µm pore size) with I / d = 150 / 4.6 mm, filled with particles with a particle size of 2.5 (the 450µm and 125µm columns) or 1.7 pm (the 45µm column) (1 pm = 1 x 10⁻⁶ m), (supplied by Waters)

[0224] 3. an Acquity APC Sample Manager - pFTN injection system

[0225] 4. an Acquity APC p-Isocratic Solvent Manager isocratic pump

[0226] The Mn and Mw values ​​were determined using Waters' Empower 3 software. 2025PF30027 - Abroad

[0227] - 35 - The number of repeat units (n in formula (5)) was determined by obtaining different peaks in the GPC which can be assigned to corresponding oligomers based on their molecular weight.

[0228] Gel permeation chromatography II:

[0229] The number-mean molecular weight (Mn) and weight-mean molecular weight (Mw) of the copoly(ester) carbonates were measured by size exclusion chromatography (SEC). A system calibration (universal calibration) was performed using a narrowly distributed PS standard: certified Mp (87200 g / mol) and experimentally determined intrinsic viscosity (IV) and refractive index increment (dn / dc) in dichloromethane from an ISO 9001 certified supplier (using GPC analysis with viscosity coupling). Dichloromethane (HPLC grade) was used as the eluent at a flow rate of 1 mL / min at 30°C. Specifically, 50 mg of the sample were dissolved in 50 mL of eluent.

[0230] Subsequently, 100 pl of the solution thus prepared were injected into the system for measurement. The GPC measurements were performed on an Agilent 1260 Infinity II system (30°C), which consisted of the following components:

[0231] 1. Agilent G7110B Isocratic Pump

[0232] 2. G7122A Agilent 1260 Degasser

[0233] 3. G7129A Agilent 1260 Sample Sampler

[0234] 4. G7116A Agilent Multicolumn Thermostat MCT with two Agilent Resipore (300 x 7.5 mm) columns

[0235] 5. G7114A Agilent 1260 variable wavelength detector

[0236] 6. G7800A Agilent 1260 GPC / SEC Multi Detector Suite with refractive index detector, viscosity detector and two-angle light scattering detector.

[0237] The Mw was determined using Agilent GPC / SEC software. The refractive index detector was used as a concentration detector.

[0238] Determination of the Tg (glass transition temperature):

[0239] The glass temperature was determined by differential scanning calorimetry (DSC) according to the standard DIN EN ISO 11357-1:2009-10 and ISO 11357-2:2013-05 at a heating rate of 20 K / min under nitrogen with determination of the glass temperature (Tg) measured as the inflection point in the second heating process.

[0240] Solution viscosity:

[0241] The relative solution viscosity (prel; also denoted as eta rel) was determined in dichloromethane at a concentration of 5 g / L at 25 °C using an Ubbelohde viscometer. (Determination 2025PF30027- Abroad)

[0242] - 36 - 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 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 3 measurements, at most 9 measurements are always taken). The actual calibration is then performed with the solvent dichloromethane. Subsequently, the polymer sample is weighed, dissolved in dichloromethane, and the flow time for this solution is then determined three times. The mean of the flow times is corrected using the Hagenbach correction, and the relative solution viscosity is calculated.

[0243] 'H-NMR spectroscopy:

[0244] The spectra were measured using a Bruker AV III HD 600 NMR spectrometer in CDCh at a measurement frequency of 600.4 MHz.

[0245] Materials used:

[0246] Cyclohexanedicarboxylic acid: 1,4-Cyclohexanedicarboxylic acid; CAS 1076-97-7 99%; Tokyo Chemical Industries, Japan, abbreviated as CHDA.

[0247] Diphenyl carbonate: Diphenyl carbonate, 99.5%, CAS 102-09-0; Acros Organics, Geel, Belgium, abbreviated as DPC

[0248] 2-Butyl-2-ethyl-1,3-propanediol, CAS: 115-84-4, > 98.5%, from Sigma-Aldrich, abbreviated as BEPD; 4-Dimethylaminopyridine: 4-(Dimethylaminopyridine; >98.0%; purum; CAS 1122-58-3; Sigma-Aldrich, Munich, Germany, abbreviated as DMAP

[0249] Isosorbide: Isosorbide (CAS: 652-67-5), 99.8%, Polysorb PS A; Roquette Freres (62136 Lestrem, France); abbreviated as ISB

[0250] Lithium hydroxide monohydrate (CAS: 1310-66-3); >99.0%; Sigma Aldrich

[0251] Lithium hydroxide, CAS: 1310-65-2, > 98.0 of TC1

[0252] Tricyclodecandimethanol: (CAS: 26896-48-0); Isomer mixture; OQ Chemicals, 40789 Monheim, Germany, abbreviated as TCD2025PF30027- Abroad

[0253] - 37 - Dimerfic acid: Pripol 1009 (CAS: 68783-41-5); Mn approx. 570 g / mol; hydrogenated, Croda, 41334 Nettetal, Germany, abbreviated as DFA

[0254] Sodium (2-ethyl)hexanoate: (CAS: 19766-89-3); 97%; Sigma-Aldrich, Munich, Germany. Tetrabutoxy titanates or titanium(IV) butoxide: CAS: 5593-70-4, > 97%; abbreviated TBT by Merck or Sigma-Aldrich.

[0255] Dibutyltin dilaurate: CAS: 77-58-7, 95%, abbreviated DBTL from Merck or Sigma Aldrich; n-Butyltin hydroxide oxide: CAS: 2273-43-0 from Merck

[0256] Ethyl acetate: CAS: 141-78-6, technical; from Merck

[0257] Dibutyltin oxide: CAS: 818-08-6, 80-90%, from Galata Chemicals, abbreviated as SUL-1 IC

[0258] Di-n-octyltin oxide: CAS: 870-08-6, >98% from Galata Chemicals, abbreviated as Mark DOTO; Monobutyltin oxide: CAS: 2272-43-0, 75-100%, from Tib Chemicals, abbreviated as MBTO or Tib cat 256

[0259] Tin(II)-2-ethylhecanoate, CAS: 301-10-0, 92.5-100.0%, from Sigma Aldrich, abbreviated as Sn(oct)2. Example 1: Polyester carbonate from DFA, TCD and ISB

[0260] 185.75 g (1.27 mol) of isosorbide, 29.18 g (0.15 mol) of TCD, 37.46 g (0.07 mol) of dimer fatty acid, and 0.02 g of tetrabutoxytitanate as catalyst were placed in a flask fitted with a distillation head. The contents of the flask were melted under a stream of nitrogen and heated to 220 °C. Water evolution was observed, with the water droplets condensing on the top of the flask and in the distillation head. A maximum of 2.52 g (0.14 mol) of water of reaction was formed. After 4.5 hours, a total salinity of 0.7 mg KOH / g was measured. The material was cooled to 120 °C, and a vacuum of 50 mbar was maintained for 15 minutes. Then, 290.3 g (1.36 mol) of DPC, 0.27 g of dibutyltin dilaurate (500 ppm), and 0.47 g of lithium hydroxide-water (500 ppm lithium hydroxide) were added. The temperature was increased, and phenol formation was observed starting at 195 °C. After holding the temperature at 195 °C for 1 h, it was slowly increased to 240 °C and held there for 1 h.The pressure was then carefully reduced to 50 mbar. The stirring speed was also reduced due to the increase in viscosity. After 2.5 hours, a brown, viscous material with a temperature of 114°C was obtained. 2025PF30027- Abroad.

[0261] - 38 - Example 2: Preparation of a compound (A) from DFA and ISB

[0262] 1071.88 g (7.33 mol) of isosorbide, 456.37 g (0.80 mol) of dimer fatty acid, and 0.15 g of tetrabutoxytitanate as a catalyst were placed in a flask with a distillation attachment. The contents of the flask were melted under a stream of nitrogen and heated to 250 °C, during which evolution of water was observed. After 2 h, the contents of the flask were cooled to 120 °C, and the concentration of ammonium chloride (COCH) was 4.9 mg KOH / g. The material was reheated to 210 °C and held under vacuum (50 mbar) for 3 h. The COCH was 3.4 mg KOH / g. The material was removed from the flask. At room temperature, a waxy, slightly brownish material was obtained. For further measurements, the material was melted, resulting in a COCH of 2.1 mg KOH / g and an oxidation-weighted oxidation state (OHZ) of 459.1 mg KOH / g.

[0263] 100 g of the material thus obtained was mixed in a flask with 100 mL of water and 100 mL of ethyl acetate and heated to 40 °C with stirring. After dissolution of the solid, the solution was allowed to cool to room temperature and the stirrer was switched off. Two phases slowly formed. They were transferred to a separatory funnel and left to stand overnight. Then the aqueous phase was separated and the ethyl acetate was removed by distillation under vacuum. A clear, slightly yellowish, viscous material remained. The oxidation state (OZ) was 3.7 mg KOH / g and the oxidation state (OHZ) was 120.4 mg KOH / g. A larger quantity ultimately yielded a material with an OZ of 3.2 mg KOH / g and an OHZ of 125.7 mg KOH / g. Figure 2 shows an ¹H NMR spectrum of this compound.

[0264] Example 3: Preparation of a compound (A) from CHDA and ISB

[0265] 1029.00 g (7.04 mol) of isosorbide, 466.29 g (2.71 mol) of CHDA, and 0.35 g of n-butyltin hydroxide oxide as a catalyst were placed in a flask with a distillation head. The contents of the flask were melted under a stream of nitrogen and heated to 250 °C, during which evolution of water was observed. After several hours, the evolution of water decreased, and a total oxidation number (TON) of 20.5 mg KOH / g and a total oxidation number (TON) of 355.7 mg KOH / g were measured. The contents of the flask were then cooled to 100 °C, and 27.4 g of isosorbide were added to compensate for the loss: the desired TON was 350 mg KOH / g. The material was heated to 210 °C and held under vacuum (50 mbar) for 2.5 h. The TON was then 9.4 mg KOH / g. The reaction was continued for another 1.5 hours at 220°C under vacuum. A brown, paste-like material formed. The total salinity (SZ) was 3.4 mg KOH / g and the total salinity (OHZ) was 346.7 mg KOH / g.

[0266] Example 4: Implementation of the compound from Example 2 using isosorbide and DPC

[0267] 10 g (0.0112 mol) of compound (A) from Example 2 were combined with 30 g (0.2053 mol) isosorbide, 46.84 g (0.219 mol) diphenyl carbonate, and 300 pl of a solution of sodium 2-2025PF30027- Abroad

[0268] - 39-ethylhexanoate (5 g in 1 l methyl tert-butyl ether) was placed in a three-necked flask equipped with a short-path separator. The mixture was freed from oxygen by fourfold evacuation and inerting with nitrogen and melted at atmospheric pressure to 160 °C with stirring.

[0269] The temperature was then increased by 20 °C at 10-minute intervals, and the stirring speed was increased. Phenol began to develop at approximately 220 °C. After reaching 235 °C, the pressure was carefully and gradually reduced to approximately 1 mbar. At 1 mbar, the mixture was stirred for another 10 minutes at a low speed. The product was then removed.

[0270] The product exhibited a solution viscosity of eta rel 1.34.

[0271] Example 5: Preparation of a compound (A) from DFA and TCD

[0272] 321.5 g (1.64 mol) of TCD, 136.9 g (0.24 mol) of dimer fatty acid, and 0.05 g of tetrabutoxytitanate as catalyst were placed in a flask with a distillation attachment. The contents of the flask were melted under a stream of nitrogen and heated to 250 °C, during which evolution of water was observed. After 2 h, the contents of the flask were cooled to 120 °C. The material was then reheated to 200 °C and held under vacuum (50 mbar) for 1 h. The total salinity was 0.9 mg KOH / g.

[0273] Example 6: Implementation of the compound from Example 2 using isosorbide, TCD and DPC

[0274] 6.19 g (0.0075 mol) of compound (A) from Example 2 were placed in a three-necked flask equipped with a short-path separator together with 16.44 g (0.1125 mol) of isosorbide, 2.94 g (0.0150 mol) of tricyclodecanedimethanol, and 29.21 g (0.1364 mol) of diphenyl carbonate, as well as 98.6 pl of a 5 g / L solution of sodium 2-ethylhexanoate in MTBE (methyl tert-butyl ether). The mixture was purged of oxygen by four cycles of evacuation and inerting with nitrogen and heated to 160 °C at atmospheric pressure with stirring. The reaction mixture was then slowly heated to 235 °C with vigorous stirring. From 220 °C onwards, phenol distilled continuously. Subsequently, the pressure was slowly reduced to <1 mbar while the temperature was simultaneously increased stepwise to 255 °C. At a pressure of <1 mbar, the mixture was stirred for 10 minutes at a low stirrer speed. The product was then removed. The product exhibited a solution viscosity of ηrel 1.350.

[0275] Example 7: Preparation of a compound (A) from CHDA and ISB

[0276] 3485.89 g (23.85 mol) of isosorbide, 1500.05 g (8.71 mol) of CHDA, and 0.45 g of TBT as a catalyst were placed in a flask with a distillation attachment. The contents of the flask were melted under a stream of nitrogen and heated to 250 °C, during which evolution of water was observed. After several hours, the evolution of water decreased, and the mixture was...2025PF30027- Abroad

[0277] - 40 - was cooled down to 220 °C and a vacuum was applied for several hours. The acid number was 4.8 mg KOH / g and the OH number 365.7 mg KOH / g. Because the OH number was too high for the intended value of approximately 250 mg KOH / g, another 69 g of CHDA was added and allowed to react with the mixture for one hour. The material was then kept at 220 °C under vacuum (50 mbar) until the acid number was below 5 mg KOH / g. A brown, paste-like material formed when poured from the reactor. The acid number was 3.7 mg KOH / g and the OH number 349.7 mg KOH / g.

[0278] Example 8: Implementation of the connection from Example 7 with DPC

[0279] 53.21 g of diphenyl carbonate and 71.73 g of compound (A) of example 7 (0.55 mol DPC in relation to the OH groups of compound (A) of example 7) were melted in an alkali-free glass flask together with the catalyst specified in Table 1.

[0280] Table 1:

[0281] Catalyst quantity in relation to compound (A)

[0282] DBTL i 500 ppm

[0283] SUL-11 i 500 ppm

[0284] Mark DOTO i 500 ppm

[0285] Sn(Oct)2 i 500 ppm

[0286] Li OH i 500 ppm

[0287] Tib cat 256 i 500 ppm

[0288] The glass flask was purged with nitrogen three times and then subjected to batch esterification under mechanical stirring. The temperature and vacuum were changed stepwise according to the following protocol:

[0289] Step 1 (50 minutes): 170 °C, atmospheric pressure

[0290] Step 2 (20 minutes): 180 °C, 200 mbara

[0291] Step 3 (40 minutes): 215 °C, 100 mbara

[0292] Step 4 (20 minutes): 240 °C, 50 mbara

[0293] Step 5 (15 minutes): 240 °C, 25 mbara

[0294] Step 6 (20 minutes): 255 °C, 5 mbara

[0295]

[0296] Step 7 (120 minutes): 255 °C <1 mbara

[0297] After step 7, the vacuum was removed and the polymer was extracted. 2025PF30027- Abroad

[0298] - 41 - The results using the different catalysts are shown in Table 2:

[0299] Table 2

[0300] Catalyst Mw (g / mol) determined via GPC method II

[0301] DBTL 18,515

[0302] SUL-11 30.821

[0303] Mark DOTO 28,819

[0304] Sn(Oct)2 9.236

[0305] LiOH 11,389

[0306] Tib Cat 256 22.214

[0307]

[0308] Example 9: Implementation of the combination of Example 7 with TCD or BEPD and DPC

[0309] 63.62 g of diphenyl carbonate, 7.17 g of 2-butyl-2-ethylpropane-1,3-diol (BEPD) or 7.17 g of TCD (see Table 4) and 71.73 g of compound (A) of Example 7 (0.55 mol DPC in relation to the sum of the OH groups of compound (A) of Example 7 and all other OH groups) were melted in an alkali-free glass flask together with the catalyst specified in Table 3.

[0310] Table 3:

[0311] Catalyst amount in relation to compound (A) LiOH j 500 ppm

[0312] DBTL + LiOH | 500 ppm

[0313] DBTL + Tib cat 256 500 ppm

[0314] Tib cat 256 : 500 ppm

[0315] DBTL 500 ppm

[0316]

[0317] The glass flask was purged with nitrogen three times and then subjected to batch esterification under mechanical stirring. The temperature and vacuum were changed stepwise according to the following protocol:

[0318] Step 1 (50 minutes): 170 °C, atmospheric pressure

[0319] Step 2 (20 minutes): 180 °C, 200 mbara2025PF30027- Abroad

[0320] - 42 - Step 3 (40 minutes): 215 °C, 100 mbara

[0321] Step 4 (15 minutes): 230 °C, 50 mbara

[0322] Step 5 (15 minutes): 240 °C, 50 mbara

[0323] Step 6 (30 minutes): 240 °C, 5 mbara

[0324] Step 7 (20 minutes): 250 °C, 5 mbara

[0325] Step 8 (75 minutes): 250 °C < 1 mbara

[0326] Step 9 (45 minutes): 280 °C < 1 mbara

[0327] After step 9, the vacuum was removed and the polymer was taken out.

[0328] The results using the different catalysts are shown in Table 4:

[0329] Table 4:

[0330] Diol catalyst Mw (g / mol) determined via GPC method II

[0331] BEPD LiOH 19,797

[0332] BEPD DBTL + LiOH 23.953

[0333] BEPD DBTL + Tib cat 256 29.182

[0334] BEPD DBTL 14.213

[0335] BEPD Tib cat 256 36.823

[0336] TCD DBTL 26.526

[0337]

[0338] Example 10: Implementation of the connection from Example 2 with DPC

[0339] 2.00 g of diphenyl carbonate and 1.50 g of compound (A) of Example 2 (0.55 mol DPC in relation to the OH groups of compound (A) of Example 2) were melted in an alkali-free test tube together with the catalyst specified in Table 5. 2025PF30027- Abroad

[0340] - 43 - Table 5:

[0341] Catalyst 1 amount in relation to compound (A) DBTL + Li OH 500 ppm

[0342] DBTL + Tib cat 256 500 ppm

[0343] DBTL 500 ppm

[0344] SUL-11 500 ppm

[0345] Mark DOTO t 500 ppm

[0346]

[0347] The glass flask was purged with nitrogen three times and then subjected to batch esterification under mechanical stirring. The temperature and vacuum were changed stepwise according to the following protocol:

[0348] Step 1 (60 minutes): 170 °C, atmospheric pressure

[0349] Step 2 (15 minutes): 180 °C, 200 mbara

[0350] Step 3 (10 minutes): 215 °C, 100 mbara

[0351] Step 4 (10 minutes): 240 °C, 50 mbara

[0352] Step 5 (10 minutes): 240 °C, 25 mbara

[0353] Step 6 (20 minutes): 255 °C, 5 mbara

[0354] Step 7 (40 minutes): 255 °C, < 1 mbara

[0355] After step 7, the vacuum was removed and methylene chloride was added to dissolve the polymer. The mixture was placed in an aluminum dish and dried. 2025PF30027- Abroad

[0356] - 44 - The results using the different catalysts are shown in Table 6.

[0357] Table 6:

[0358] Catalyst Mw (g / mol) determined via GPC method II

[0359] DBTL + LiOH 23,497

[0360] DBTL + Tib cat 256 15.458

[0361] DBTL 16,682

[0362] SUL-11 73.132

[0363] Mark DOTO 17,784

[0364]

[0365] As the results show, copolyester carbonates can be efficiently produced using the inventive process. Furthermore, the copolyester carbonates exhibit an excellent carbon balance.

Claims

2025PF30027- Abroad Patent claims:

1. A process for producing an amorphous polyester carbonate with a glass transition temperature > 90 °C, comprising the steps (i) Esterification of a 1,4:3,6-dianhydrohcxitol and / or of tricyclodecanedimethanol with at least one dicarboxylic acid and / or an anhydride of a dicarboxylic acid to obtain a compound (A) having at least two ester groups and an acid number of less than 10 mg KOH / g and (ii) Reaction of compound (A) with at least one diaryl carbonate and / or dialkyl carbonate to obtain the polyester carbonate.

2. Method according to claim 1, characterized in that at least one additional diol is present in method step (ii).

3. Method according to claim 2, characterized in that the at least one additional diol is aliphatic or cycloaliphatic.

4. The method according to claim 3, characterized in that the at least one additional diol is selected from the group consisting of 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2-bis(4-hydroxycyclohexyl)propane, tetrahydro-2,5-furandimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, cyclobutane-1,1-diyldimethanol, and 8-(hydroxymethyl)-3-tricyclo[5.2.1,02,6]decanyl]methanol, 2-butyl-2-ethyl-1,3-propanediol, 2-(2-hydroxyethoxy)ethanol, 2,2,4-Trimethyl-1,3-pentanediol, 2,2-Dimethylpropane-1,3-diol, 1,2-Propanediol, 1,3-Propanediol, 1,4-Butanediol, 1,5-Pentanediol, 1,6-Hexanediol, 1,8-Octanediol, 1,4:3,6-Dianhydrohexitol and a compound of formula (4), HO-(CH2) r -R3-(CH2) s -OH (4) where each r and each s independently represents a number between 0 and 4, and each R 3independently of each other stands for a structure of the formulas (R3A), (R3B), (R3C) and (R3D). (R3A), where a is 0 or 1, 2025PF30027- Abroad (R3B), where b is 0 or 1, (R3C), where the positions marked with , in formulas (R3A) to (R3D) are the positions where the (CfFf group or (CfFjs group) shown in formula (4) is located.

5. The method according to claim 4, characterized in that the at least one additional diol is selected from the group consisting of 1,4:3,6-dianhydrohexitol and a compound of formula (4), wherein in formula (4) each r and each s are independently assigned a number between 0 and 2, most preferably 0 or 1, and each R 3 independently of each other stands for a structure of the formulas (R3A) and a is 0 or 1.

6. A method according to any one of claims 1 to 6, characterized in that the dicarboxylic acid is selected from the group consisting of the compounds represented by formula (1), (2) and (3), sebacic acid, furandicarboxylic acid, naphthalendicarboxylic acid, phthalic acid, isophthalic acid and terephthalic acid or the corresponding anhydrides of the aforementioned acids, wherein in formulas (1) and (2) B each independently of each other stands for a CFF group or a heteroatom selected from the group consisting of O and S, preferably a CH2 group or an oxygen atom, 2025PF30027- Abroad - 47 - Ri each independently of each other stands for a single bond or an alkylene group with 1 to 10 carbon atoms, preferably a single bond or an alkylene group with 1 to 5 carbon atoms, in particular preferably a single bond, and n is a number between 0 and 3, preferably 0 or 1, and OO H° OH (3X wherein in formula (3) each R 2 independently of each other stands for an aliphatic group with 16 to 44 carbon atoms, which may contain one or more double bonds.

7. Method according to any one of claims 1 to 6, characterized in that the dicarboxylic acid is aliphatic.

8. Method according to one of claims 6 or 7, characterized in that R 2 The formula (3) is represented by the following formula (R2A) with CH3 R 11 - R 11 — Y— R 11 - I R11 I CH3 (R2A), where Y represents a bridging structure selected from the group consisting of an alkylene group with 1 to 4 carbon atoms, an alkylidene group with 1 to 4 carbon atoms, and a cycloalkylene group with 4 to 12 carbon atoms, wherein the cycloalkylene group optionally contains one or more double bonds and / or is optionally fused to one or more further cycloalkylene groups, wherein the one or more further cycloalkylene groups optionally each have one or more double bonds, 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 each other, represents an alkylene group with 1 to 12 carbon atoms or an alkylidene group with 1 to 12 carbon atoms, provided that the structure of formula (R2A) comprises 16 to 44 carbon atoms and wherein the positions marked with , in formula (R2A) are the positions at which the (C=O) groups shown in formula (3) are located, which are attached to R 2 adjacent. 2025PF30027- Abroad - 48 - 9. Method according to claim 8, characterized in that the formula (R2A) is represented by one of the formulas (R2Aa), (R2Ab), (R2Ac) or (R2Ad), with CH— CH (R2Aa), (R2Ab), where each R 11 and each the meanings mentioned in claim 8, the cycle of formula (R2Ac) optionally has one or two double bonds and each cycle of formula (R2Ad) optionally contains one or two double bonds independently of each other.

10. Combination of formula (5) — — n (5) where in formula (5) each A independently represents formula (5a) or (5b), (5a), (5b), where the where the with The marked positions in formulas (5a) and (5b) are the positions where the oxygen atoms shown in formula (5) are located, adjacent to A. each R 2 independently of each other stands for an aliphatic group with 16 to 44 carbon atoms, which may contain one or more double bonds and n represents a number from 1 to 10. 2025PF30027- Abroad - 49 - 11. Polyester carbonate comprising the structural unit of formula (6) (6) where in formula (6) Z always stands for either formula (5a) or formula (5b), Each A independently represents formula (5a) or (5b), (5a), (5b), where the where the with The marked positions in formulas (5a) and (5b) are the positions where the oxygen atoms shown in formula (6) are located, which are adjacent to A or Z, the positions marked with in formula (6) are the positions at which formula (6) is incorporated into the polyester carbonate, each R 2independently of each other stands for an aliphatic group with 16 to 44 carbon atoms, which may contain one or more double bonds and n represents a number from 2 to 10.

12. Compound according to claim 10 or polyester carbonate according to claim 11, characterized in that R 2 represented in formula (5) or formula (6) is represented by the following formula (R2A) CH3 R 11 - R11 — Y — RH - I R 11 I CH3 (R2A), where Y represents a bridging structure selected from the group consisting of an alkylene group with 1 to 4 carbon atoms, an alkylidene group with 1 to 4 carbon atoms, and a cycloalkylene group with 4 to 12 carbon atoms, wherein the cycloalkylene group optionally contains one or more double bonds and / or 2025PF30027- Abroad 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, where the R adjacent to the bridging structure 11 -groups are bound to any position of the bridging structure and where each R 11 independently of each other, represents an alkylene group with 1 to 12 carbon atoms or an alkylidene group with 1 to 12 carbon atoms, provided that the structure of formula (R2A) comprises 16 to 44 carbon atoms and wherein the positions marked with , in formula (R2A) are the positions at which the (C=O) groups shown in formula (5) or (6) are located, which are attached to R 2 adjacent.

13. Compound according to claim 12 or polyester carbonate according to claim 12, characterized in that the formula (R2A) is represented by one of the formulas (R2Aa), (R2Ab), (R2Ac) or (R2Ad), with H3C ~ H3C ~ R 11 R 11 R 11 R 11 / CH-CH R11 \l1 R11 Rl^ CH 3 3 (R2Aa), (R2Ab), where each R 11 and each the meanings mentioned in claim 11, the cycle of formula (R2Ac) optionally has one or two double bonds and each cycle of formula (R2Ad) independently optionally contains one or two double bonds.

14. Molding compound containing the polyester carbonate according to claim 11.

15. Molded body containing the polyester carbonate according to claim 11.

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